Reductive deoxygenation of alcohols is particularly challenging because of the high bond dissociation energy of the C−OH bond and the poor leaving ability of the hydroxyl group. Herein we describe a Ph 3 P�O-catalyzed reductive deoxygenation of benzyl alcohols with PhSiH 3 under an air atmosphere within 30 min of reaction time. The use of catalytic loading of Ph 3 P�O enhances the practicality of this protocol.