Pepe Reina was an unused substitute as World Cup holders Spain were shocked by a comeback from the Netherlands, who secured an incredible 5-1 victory in Salvador.
Former Liverpool midfielder Xabi Alonso earned Spain a lead on 27 minutes, drilling home a low spot-kick into the left corner from 12 yards.
The Netherlands hauled themselves level a moment before half-time, however - Robin van Persie redirected a precise long pass over the goalkeeper with his head for 1-1.
Arjen Robben completed a Dutch turnaround when he calmly controlled a through ball, cut inside his marker and powered home from close range eight minutes into the second half.
And there was more to come; defender Stefan de Vrij met an inswinging set-piece at the back post and bundled the ball over the line to stun the defending champions.
With 20 minutes remaining, the Netherlands remarkably grabbed a fourth. Van Persie capitalised on a mistake by Spanish goalkeeper Iker Casillas and toe-poked in.
Robben had the final say on proceedings, streaking into space with searing pace, composing himself under pressure and slamming into the back of the net.
Spain will continue their Group B challenge next Wednesday, when they take on Chile in Rio de Janeiro. The Netherlands meet Australia on the same day.