Abstract: A palladium catalyzed chemo- and enantioselective hydrogenation and hydrogenolysis of α-acyloxy ketones for the synthesis of chiral α-acyloxy-l-arylethanols, simple ketones and chiral α-acyloxy ketones, has been realized. The chiral products have the potential to be transformed to various biologically active compounds and chiral drugs. S/C ratios up to 5000-6000 are obtained, and this homogeneous palladium catalyzed asymmetric hydrogenation has good prospects for use in industry.