The Spaniards saw the defence of their crown get off to a disastrous start last week as they were dismantled 5-1 by the Netherlands.
While a draw with Chile would keep their hopes of reaching the second round alive, Vicente del Bosque's team ideally need a victory to kickstart their campaign.
However, they are up against a Chilean side that is full of confidence following a 3-1 win in their opening match of the tournament against Australia.
The South Americans head into the clash with Spain knowing that a victory would all but secure them a place in round two.
Spain captain Iker Casillas's place in the side has been in doubt after his disappointing display versus the Dutch, but the shot-stopper is likely to keep his spot after David de Gea suffered a hip injury in training.
The world champions have no other fitness concerns, but Del Bosque has suggested that he could make multiple changes to his starting XI.
Chile are expected to name the same team that saw off the Aussies, with Barcelona forward Alexis Sanchez leading their attack.
Possible starting lineups
Spain: Casillas; Azpilicueta, Pique, Ramos, Alba; Busquets, Alonso, Xavi; Silva, Torres, Iniesta
Chile: Bravo; Isla, Mena, Diaz; Medel, Jara, Aranguiz, Vidal, Vargas; Sanchez, Valdivia
Sports Mole says: 2-1