In conclusion, a highly enantioselective cobalt-catalyzed hydro-semipinacol rearrangement of allylic alcohols involving 1,2-aryl migration has been established. We demonstrated that alkylcobalt(IV) species can mimic the electrophilic behaviour of a secondary carbocation whilst providing a chiral environment to dictate the stereochemical outcome of the reaction. The polar nature of the rearrangement was probed by a Hammett analysis, which confirmed the preferential migration of the most electronrich aryl group. This protocol provides facile access to desirable a-aryl ketones bearing tertiary stereocenters with excellent enantioselectivities (up to 99 : 1 er) and high yields, except for substrates containing ortho-substituted aromatic rings.