A novel and efficient decarboxylative alkynylation of N-(acetoxy)phthalimides of α-amino acids with terminal alkynes has been developed by merging photoredox with copper catalysis at room temperature, and the reaction provided the valuable propargylamines in good to excellent yields with assistance of [Ru(bpy)3]Cl2/CuI and visible light. The simple protocol, mild reaction conditions, and high efficiency of this method make it an important strategy for synthesis of diverse molecules containing amino acid fragments.