Group B kicks off with a rematch of the 2010 World Cup final as Spain will take on the Netherlands at the Arena Fonte Nova on Friday.
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The two countries needed extra time to decide the winner of the 2010 final, which Spain ultimately won thanks to an Andres Iniesta strike.
And with the majority of the same pieces in place, Spain will be looking to make history by not only becoming the first nation to claim back-to-back World Cup titles since Brazil achieved the feat in 1962, but also by becoming the first European country to win the tournament in South America.
Spain's 2010 campaign opened with a narrow defeat to Switzerland, so with a much more difficult opponent awaiting the reigning champions in their 2014 opener, Bayern Munich midfielder Javi Martinez attempted to take some pressure off the team.
"In 2010 we showed that if you lose the first game it's not all over, but we want to get off to a winning start," he said. "To win the tournament you have to win as many games as possible, but in the last World Cup we showed that even after losing the first game, we wanted to get to the final."
While Spain remains among the favorites to win the entire tournament, the Netherlands faces stiff competition to emerge from a cutthroat field in Group B, which also consists of Chile and Australia.
The Dutch have plenty of experience in attack with the likes of Robin van Persie, Arjen Robben and Wesley Sneijder, but the back line is relatively untested, increasing the concern as to whether the 2010 runners-up can even make it out of the group this time around.
In order to compensate for the lack of experience in defence, manager Louis van Gaal looks poised to deploy five defenders in the form of three center-backs and two wing-backs.
Ron Vlaar, who should feature as one of the nation's three central defenders along with Stefan de Vrij and Bruno Martins Indi, is aware of the perception of Holland's weak defence, but he was quick to point out the stout performances in qualifying that saw the Dutch concede just five goals in 10 group games.
"We know that. We work hard to get better as a team and we also know we have our best players up front," Vlaar said. "But if you look at all the games we played during qualification and friendlies we didn't concede many goals.
"So we have to give confidence to our forwards to accelerate and make a difference for us. You play every game to win. You have to be realistic but I really believe we can achieve something. I look forward to it and I cannot wait."
Mexico ready to put sloppy qualifying in the past vs. Cameroon
After an absolutely dismal qualifying campaign, Mexico will get its first chance to put that struggle in the rearview mirror on Friday against Cameroon in Group A play at the Estadio das Dunas.
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Mexico struggled mightily in CONCACAF qualifying, finishing fourth and needing a gift from the United States just to reach Brazil.
El Tri was on the verge of staying home before the United States, which had already qualified for the World Cup, scored in stoppage time against Panama in the final round of matches to help Mexico clinch fourth place.
A fourth-place finish meant El Tri faced New Zealand in a two-legged playoff, but breezed past the All Whites, 9-3, on aggregate to avert disaster.
Head coach Miguel Herrera, who was installed as the team's fourth head coach during qualifying, will be hoping his side can put that difficulty in the past and focus on getting out of a tough group.
Herrera has only been in charge for about six months, and he is taking a bit of a gamble by pinning Mexico's hopes on 35-year-old defender Rafael Marquez, who will become the first player to captain his side at four different World Cups.
Javier Hernandez is a familiar face up top for Mexico, but the team will also rely on some new blood as well with Oribe Peralta leading the team in goals in qualifying while Carlos Pena carved out a place in the midfield for himself with some strong performances recently.
But El Tri will be without a pair of players in Luis Montes and Juan Carlos Medina.
Medina, 31, figured to occupy a defensive role in the middle of the field but who will miss the tournament because of an ankle injury, while Montes will miss the tournament with a broken leg suffered in a friendly against Ecuador.
Cameroon, meanwhile, will be making its seventh appearance in the World Cup hoping to replicate the success they had 24 years ago.
The 1990 team stunned the rest of the world by becoming the first African side to reach the quarterfinals at the World Cup as they were led by the scoring exploits of veteran striker Roger Milla.
Head coach Volker Finke's team will be trying to break a streak of four straight group-stage exits.
The Indomitable Lions are led by 32-year-old forward Samuel Eto'o.
Eto'o has been in and out of the side in recent years, but enters the World Cup in fine form after scoring nine goals in 21 appearances for Chelsea last season.
Eto'o has netted three World Cup goals in his career, leaving him two short of Milla's record for the national team, and he may need to match that total if the team is going to finish in the top two in Group A.
Vincent Aboubakar and Pierre Webo will also be expected to share some of the scoring load, while Alex Song, Stephane Mbia and Jean Makoun make up a quality midfield.
With Brazil and Croatia also in Group A Friday's match is crucial for both clubs. Mexico will be hoping to get off to a good start with three points, while Cameroon will also need three points if they hope to escape the group stage.
Chile has plenty to prove in World Cup opener vs. Australia
Chile will have its first opportunity to open the eyes of the football world on Friday against Australia in Group B play at the Arena Pantanal.
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La Roja arrived on the world football scene in 2010 when they showed the can play as beautifully as any team in South Africa. Under Marcelo Bielsa, the team was full of vibrancy and vigor, attacking with a fluidity that not many expected.
Chile's squad remains largely unaltered from 2010 and are led by key pieces such as Mauricio Isla, Gary Medel and Alexis Sanchez.
Sanchez has made the jump from promising player to global superstar. The 25- year-old enjoyed a banner year with Barcelona, scoring 19 goals in league play.
Isla, 25, has gained much more experience since his exploits at the 2010 World Cup, splitting his club allegiances with two seasons at Udinese before making the switch to Juventus in 2012.
The same can be said for Medel, who was a key defender for Sevilla in a run of a few impressive seasons. The 26-year-old moved to Cardiff City last summer, and while the Welsh club was relegated from the Premier League, Medel enjoyed a solid campaign on a personal level.
On the offensive end, Esteban Paredes, Mauricio Pinilla, Eduardo Varas, Jean Beausejour and Fabian Orellana all have a chance to chip in as Sanchez cannot be expected to carry the team out of a group that consists of Spain, Australia and the Netherlands.
The biggest question for Chile will be whether midfielder Arturo Vidal is fit for the opening match. Vidal is one of the most well-rounded central midfielders in the world, but he was a surprising inclusion on the final roster following a recent knee operation.
Chile is more than capable of making it out of Group B without Vidal, but its outlook would be much brighter if the Juventus man is able to suit up.
Australia, meanwhile, enters the 2014 event as a huge underdog against stiff competition in the group.
And facing teams like Spain, Chile and The Netherlands with a vastly inexperienced squad doesn't make the Socceroos task any easier.
Tim Cahill and Mark Bresciano are the only two members of the team with more than 50 caps, making them two of the country's most important pieces.
Cahill has featured for Australia in 2006 and 2010 and even became the first Australian player to score in World Cup play by netting two goals against Japan on June 12, 2006.
Bresciano, also 34, boasts a great deal of experience in Serie A having represented the likes of Parma, Palermo and Lazio, but he has not played in Italy's top flight since 2011.
Captain Mile Jedinak is another key piece for the Socceroos. He is coming off an impressive season in the Premier League with Crystal Palace and will be tasked with guiding the team from the middle of the park.
Australia figures to struggle in Group B, but Friday's match represents the club's best chance to earn a point.