It was proved that a judicious choice of counteranion played a prominent role in Cu(II) catalysis for enantioselective boron conjugate additions in water; the use of Cu(OH)2 renders heterogeneous catalysis, whereas Cu(OAc)2 renders homogeneous catalysis; cyclic dienones underwent a remarkable switch of regioselectivity between 1,4- and 1,6-modes of the additions through these catalyses.