This paper describes a NaPHI-catalyzed oxytrifluoromethylation of olefins under photoirradiation. The reaction is applicable for the synthesis of α-trifluoromethyl ketones, which could be structurally elaborated into an array of useful scaffolds. Mechanistic studies suggested that photoexcited NaPHI* could facilitate the formation of singlet 1O2 through an EnT process, thus enabling difunctionalization with trifluoromethyl radical and oxygen radical anion species.