Highly enantioselective dialkylzinc addition to a series of aldehydes was developed based on chiral Zn(II)-BINOLate catalysts bearing phosphonates [P(=O)(OR)2] and phosphoramides [P(=O)(NMe2)2] at the 3,3′-positions. The reactions proceeded smoothly and showed reductions in the amounts of both catalysts and dialkylzinc reagents to be loaded.