An unprecedented deoxygenative gem-difluorovinylation of aliphatic alcohols using α-trifluoromethyl alkenes is achieved under photocatalytic conditions. Inexpensive Ph3P acts as an efficient O-atom transfer reagent to facilitate the deoxygenation of alcohols for the generation of reactive alkyl radical species. Remarkable features of this reaction include mild conditions, simple operation and broad scope. The synthetic utility of this reaction was validated by the success of two-step one-pot reactions, scale-up synthesis and chemoselective monodeoxygenation of diols.