A novel Pd(II)-catalyzed enantioselective oxycarbonyl-ation of alkenes has been established herein. The ligand with an ethyl group at the C-6 position of Pyox plays a significant role in the intermolecular oxypalladation process, leading to high reactivity and excellent enantioselective control. Compared to the conventional methods, the reaction itself features alkenes as easily prepared starting materials, mild and operationally simple reaction conditions, and insensitivities to air and water. Moreover, this method allows for broad alkene substrate scope, excellent regio- and enantio-selectivities, scalabilities and a wide array of applications, and provides a useful route for the convenient and straightforward synthesis of chiral s -hydroxy alkylcarboxylic acids/esters.