The catalytic asymmetric copper-catalyzed conjugate addition of diethylzinc to α,β-unsaturated acylsilanes was found to proceed smoothly in moderate to good yields and promising enantioselectivities (up to 85% ee) in the presence of the multifunctional HZNU-Phos with both a phosphine center and BINOL-based diol moiety that played a crucial role in the achievement of the best enantioselectivity for this reaction.