Argentine forward Carrillo - on loan from Southampton - had the opportunity to score from 12 yards after Mario Gaspar committed a foul in the area.
Rolán tried his luck from the edge of the area, and the ball struck the hand of the Villarreal right-back.
Carrillo took on the responsibility and sent the ball flying into the stands, far wide of Sergio Asenjo's goal.
Until today, in LaLiga there had been 10 penalties given and all of them had resulted in goals, though Carrillo has broken the trend.