The chiral binaphthol-catalyzed enantioselective conjugate addition of alkynyl trifluoroborates to cyclic N-sulfonyl ketimines is reported, providing β-alkynyl imines bearing a propargylic stereocenter in high yields and excellent enantiomeric purities (up to >99% ee). This mild, scalable catalytic system exhibits high efficiency and broad substrate scope. Additionally, heteroaryl trifluoroborates and aryl trifluoroborates were viable nucleophiles under standard conditions.