The regioselective and enantioselective Cu(II)-catalyzed 1,4-conjugate addition of diethylzinc reagent to nitrodienes is described. With 0.25 mol % of Cu(OAc) 2 and chiral amidophosphine ligand L3, the 1,4-addition products were produced with a complete regioselectivity, high yields (81−98%), and excellent enantioselectivities (87−97% ee) in a short reaction time.