Defending World Cup champions Spain and 2010 runners-up Netherlands appear to be favourites to emerge from a highly competitive pool of teams as last-16 qualifiers, but Group B provides one of the more unpredictable narratives of Brazil 2014.
Expectations surrounding Australia may have dimmed after their daunting draw against two of the tournament favourites, but the Socceroos are always capable of springing a surprise in the heat of battle.
Meanwhile, Chile confirmed they have class and quality in abundance with their impressive surge of wins to secure qualification, not to mention their convincing 2-0 win against England at Wembley last November.
It may be that Jorge Sampaoli's Chile hold the key to this group. In South American conditions, Chile's attack-minded team are being tipped by many observers to emerge as a surprise team in this World Cup, but if they are to live up to their pre-tournament hype, a victory against either the Netherlands or Spain will need to be delivered. That will be no easy task.
The opening Group B game between Vincente Del Bosque's Spain and Louis van Gaal's Netherlands in San Salvador on June 13 has the potential to emerge as the most sumptuous feast of the opening phase of the tournament.
The two sides that played out the last World Cup final four years ago are oozing with class and experience, with the knowledge both have of each other adding to the fascination of a clash that will test the resolve of both nations from the moment they hear the first whistle in Brazil.
Spain's shock defeat against Switzerland in their opening match of South Africa 2010 confirms this team of champions can be slow starters, yet the sight of a potent, dangerous Dutch side should fire their burners this time.
While both nations may be content with a draw from that high profile opening game, they could find themselves in a perilous position in the group if Chile record a victory against Australia in their opening match.
Diego Costa (Spain): The newest addition to Spain's all-conquering team of champions has the potential to give them a new dimension at this World Cup, but only if he can fight back from injury. Brazilian-born Costa was a star of Atletico Madrid's stunning season but will need to overcome a hamstring tear if he wants World Cup glory.
Robin van Persie (Netherlands): Dutch coach Louis van Gaal sees Manchester United striker Van Persie as his key performer, and now it is up to the 30-year-old who has a penchant for spectacular goals to confirm his worth when it matters most.
Alexis Sanchez (Chile): This may not have been a vintage season for Barcelona, but their Chilean World Cup star emerged from the disappointment at the Nou Camp with his reputation intact. His adoring public in Chile will expect him to carry his nation to World Cup glory.
Tim Cahill (Australia): The New York Red Bulls attacking midfielder needs to produce goals for his country against demanding opposition in Brazil. His scoring record against the strongest of opponents during his time at Everton in the Premier League was impressive.
What Matters Most
Goalscorers litter the Group B landscape and it may be that the striker who catches fire from the start can guide his team to success in a series of games that offers up delightful uncertainty.
Spain's Diego Costa has proved he has the power, drive and ability to test the best of defences, but he has yet to prove the form he has shown at Atletico Madrid can be converted to a World Cup stage.
Then there is the duo of Robin van Persie and Arjen Robben, who may take part in their own duel to earn top billing in a traditionally combustible Dutch team, with both capable of exploding into life and destroying the best of opponents.
The Chilean attacking triumvirate of Alexis Sanchez, Eduardo Vargas and Jorge Valdivia are also potency personified in front of goal, and in a pool where defending is not the strong suit of the teams involved, goals is the currency likely to reap handsome rewards.
Group B features Spain and the Netherlands, both finalists from the 2010 World Cup. That makes this the first time the two previous World Cup finalists have met in the ensuing Group Stage.