Vicente del Bosque's men arrived in Brazil as one of the pre-tournament favourites having triumphed in South Africa four years ago, as well as retained their UEFA European Championship title in 2012.
However, Spain's World Cup defence began in a disastrous fashion as Louis van Gaal's side stormed to a shock 5-1 Group B victory in Salvador on Friday.
Xabi Alonso's 27th-minute penalty had appeared to put Spain in a strong position, but Robin van Persie's superb headed equaliser shortly before the break triggered a second-half demolition from the Dutch.
Central defensive pair Sergio Ramos and Gerard Pique as well as Brazil-born striker Diego Costa also faced scrutiny for their performances, but it remains to be seen if Del Bosque will change his line-up or hand an opportunity to the side that failed so spectacularly last week.
It is the second time in as many World Cups that the teams have faced off, Spain triumphing 2-1 in 2010, although both sides still progressed from Group H.
"We have strong faith in our football, in our ideas and we really believe we can overcome the situation," he said. "This group is like a family since I arrived here.
"I think it's vital this kind of friendship between all of us, this familiar feelings which have made the Spain national team into a successful team."
Chile started their campaign with a 3-1 victory over Australia, but that scoreline somewhat belied the difficulty that Jorge Sampaoli's side faced in Cuiaba.
The South Americans were fluent in attack, with Barcelona forward Alexis Sanchez particularly lively, yet goalkeeper Claudio Bravo was required to make a series of saves to deny Australia at least a draw.
"We're going to push forward looking for the three points," he said. "We have our style and we'll keep to it, we'll keep working in the same way and we're not going to change that."
