A photocatalytic hydroalkoxylation reaction enables the coupling of aliphatic alcohols with gem-difluoroalkenes, expanding the scope of accessible α,α-difluorinated ethers, a desirable substructure for medicinal and agricultural chemists. This reaction exploits an uncommon diselenide co-catalyst to facilitate the net hydrofunctionalization process, which contrasts alternate single-electron reactions that deliver dioxidation products. Future use of this co-catalyst might enable other currently unknown photocatalytic reactions.