Chiral Al/Zn heterobimetallic complexes are effective catalysts for the direct highly enantioselective aldol reaction of acetophenones with aromatic aldehydes. The Al site in the complex acts as a Lewis acid to activate aldehyde, whereas ethylzinc alkoxide plays a role of a Bronsted base to form a reactive zinc enolate with acetophenone. Distinct nature of two different metals contributes to the efficient direct asymmetric aldol reaction.