We report herein an efficient four-component photoredox-catalyzed reaction. Under the optimized conditions using [Ru(bpy)3(PF6)2] as the photocatalyst, a wide range of terminal and internal alkenes can efficiently undergo azidoalkoxy-trifluoromethylation in the presence of Umemoto's reagent, carbonyl compound, and TMSN3, giving rise to original and highly complex molecules in a single operation.