A series of novel chiral diphosphite ligands have been synthesized from (1R,2R)-trans-1,2-cyclohexanediol, (1S,2S)-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand (1R,2R)-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediol 6a′ derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.