The homolytic cleavage of C-O bonds to afford alkyl radicals is an attractive yet challenging transformation in organic synthesis. Herein we describe a photocatalyzed deoxygenative C-C coupling reaction of xanthate salts, which can be easily prepared from the corresponding alcohols. The key to the success of this strategy is the low oxidation potential of the xanthate salt and the use of an appropriate phosphine to accelerate the desulfurative release of carbonyl sulfide.