Development of catalytic generation of allyl–metal complexes through allylic C–H cleavage of alkenes without prefunctionalization followed by site- and stereoselective carbon–carbon bond formation is of great importance in organic synthesis, providing a straightforward and step-economical approach to introduce a versatile allyl group into organic molecules. Although significant advances have been achieved in enantioselective transformations of electrophilic allyl–metal complexes and allyl radicals, enantioselective reactions of nucleophilic allyl–metal intermediates furnished through allylic C–H cleavage remain undeveloped. Herein, we identify a multi-tasking chiral catalyst derived from a commercially available phosphine ligand and cobalt salt that precisely controls the chemoselective formation of the allyl–cobalt complex and the site- and stereoselective addition to carbonyls, delivering a broad scope of homoallylic alcohols with high yield and stereoselectivity. This work may establish a platform for the development of enantioselective transformations of nucleophilic organometallic complexes generated from catalytic C–H functionalization.