A series of Cu (II) complexes bearing asymmetric derivatives of (R,R)‐1,2‐diaminocyclohexane were synthesised and characterised. The X‐ray structures of the complexes showed distorted square planar geometry. The catalytic activities of in situ‐generated copper acetate complexes in the presence of 10 mol% of N,N‐diisopropylethylamine were evaluated in the asymmetric Henry reaction. The current catalysts showed high enantioselectivity (up to 99%) for (S)‐1‐nitro‐4‐phenylbutan‐2‐ol from the reaction of 3‐phenylpropanal and nitromethane.