Spain will look to bounce back from the mauling handed out by the Netherlands, while Holland will look to continue their brilliant start to the FIFA World Cup 2014, when tricky Group B takes centre-stage on Wednesday.
Apart from Spain's must-win match against Chile and the Netherlands' game against Australia, there will also be a Group A match between Cameroon and Croatia, both teams looking to pick up their first victory in the tournament after disappointing opening defeats.
All eyes will be on Spain, though, to see just how the defending champions respond from that unbelievable 5-1 thrashing handed out by the Dutch.
Spain were just plain and simple outplayed by an incredible wave of Holland's attacking players, with the defence unable to cope with the intense pressure. Things will need to change for Spain against Chile, a team they have never lost to, but also a team easily capable of topping the European champions with their quickfire attacks.
Before Spain takes the field against Chile at the Maracana in Rio de Janeiro, the Netherlands will look to make it two wins out of two with three points against Australia in Porto Alegre.
Robin Van Persie and Arjen Robben were in irresistible form for Holland against Spain, and if the duo put up a similar performance against Australia, a team they have never beaten, then Ange Postecoglou's team could be in for a hiding.
Australia, though, were quite impressive against Chile, despite their 3-1 loss and will take heart from that performance. However, they will know that even if they are at their best, if Holland bring out the big guns, then the result will go only one way.
Rounding off the action on Wednesday will be Cameroon and Croatia, with the two teams looking for their first points in Group A.
While Cameroon were quite disappointing against Mexico in their opening encounter, Croatia were extremely unlucky to come away from their match against hosts Brazil without anything to show for it.
That penalty decision will still be rankling the Europeans, but if they put in a performance similar to the one against Brazil, perhaps with a little bit more cutting edge, then they should be able to get past Cameroon.
Cameroon, on the other hand, will have to find quality which they were seriously lacking against Mexico, and that too most probably without their talisman and skipper Samuel Eto'o.
FIFA World Cup Schedule:
Australia vs Netherlands at the Estadio Beira-Rio in Porto Alegre (1 pm local time, 9.30 pm IST, 5 pm BST, 12 pm ET).
Spain vs Chile at the Maraca in Rio de Janeiro (4 pm local time, 12.30 am IST, 8 pm BST, 3 pm ET).
Cameroon vs Croatia at the Arena Amazonia in Manaus (6 pm local time, 3.30 am IST, 11 pm BST, 6 pm ET).