Molinari picked up his third win on the European Tour on 6 May 2012 at the Reale Seguros Open de España. He was four strokes out of the lead going into the final round but fired a 65 (−7), the best round of the tournament, to win by three strokes over Alejandro Cañizares, Søren Kjeldsen and Pablo Larrazábal. In July 2012, the week before the Open Championship, Molinari lost in a playoff at the Aberdeen Asset Management Scottish Open. He was defeated on the first playoff hole by Jeev Milkha Singh.