The Product of isophorone(IP) asymmetric hydrogenation, i.e., chiral (R- or S-) 3,3,5-trimethylcyclohexaone (TMCH), is foremost significance fine chemicals intermediates. In the paper， that the asymmetric hydrogenation of isophorone and the catalytic hydrogenation kinetic resolution of TMCH catalyzed by Pd/Al2O3 catalyst in the presence of (L)-proline was investigated. It was shown that the condensation product formed from the pretreatment of the reaction mixture of isophorone with (L)-proline indeed inhibited the asymmetric hydrogenation of isophorone. The spontaneous monolayer dispersion of (L)-proline appeared very easily on the surface of Pd/Al2O3 catalysts, and this phenomenon could effectively increase TMCH enantiomeric excess (ee) from the hydrogenation of TMCH. The ee % of TMCH hydrogenation product was as high as 100 % from the Pd/Al2O3 catalyst modified by the monolayer dispersion of (L)-proline at 40 ℃, and under hydrogen pressure 1 MPa for 10 hrs.