A Direct multicomponent oxidative addition of CF₃ and H₂O to diverse alkynes was achieved with photoredox catalysis to obtain α-trifluoromethyl ketones via rapid enol-keto tautomerization of the adducts. The reaction exhibits high functional group tolerance, operational simplicity and regioselectivity. Various sizes trifluoromethylated heterocycles were synthesized from the α-CF₃ substituted diketone product obtained through our protocol, thereby demonstrating the versatile applicability of the method. Mechanistic studies of the reaction with isotope labelled experiments provided insight into the reaction pathway.