A direct catalytic asymmetric addition of allyl cyanide to ketones with a bimetallic catalytic system comprising (R,R)-Ph-BPE/[Cu(CH3CN)(4)]ClO4/LiOAr is described. Exclusive gamma-addition of allyl. cyanide was observed, affording optically enriched tertiary alcohols bearing Z-configured a,B-unsaturated nitrites. The reaction proceeded under proton-transfer conditions, utilizing soft Lewis acid/hard Bronsted base bifunctional catalysis. The applicability of the reaction to aromatic, heteroaromatic, and aliphatic ketones demonstrates its wide substrate generality.