Herein, we report a catalytic enantioselective addition of C-alkynyl imines with hydroperoxides catalyzed by chiral BINOL calcium phosphate, affording a broad range of enantioenriched α-peroxy propargylamines in good yields (80–99%) with high enantioselectivities (up to 94% ee). The protocol is characterized by mild conditions, easy accessibility and good practicability.