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 Ph3P═O-catalyzed reductive deoxygenation of benzyl alcohols with PhSiH3 under an air atmosphere within 30 min of reaction time. The use of catalytic loading of Ph3P═O enhances the practicality of this protocol.