Cr(salen) complex 3 was found to be an efficient catalyst for asymmetric addition of allyltributylstannane to non-branched aliphatic aldehydes, giving the corresponding homoallylic alcohols in a highly enantioselective manner. For example, its addition to 3-phenylpropanal and 6-phenoxyhexanal proceeded with 92 and 94% ees, respectively, under atmospheric pressure.