Chiral catalytic film, PLPy (Pd) electrodes, which were coated with poly (N-substituted pyrrole) film having l-(+)-lactic acid moiety as an optically active group and were incorporated with palladium catalytic metal were prepared. By use of these electrodes, the electrocatalytic hydrogenation of α-keto ester compounds, methyl benzoylformate (1a) and butyl benzoylformate (1b) in an ethanol-HCl buffer solution led to efficient formation of the corresponded hydrogenated products, (R)-(−)-methyl mandelate (2a) and (R)-(−)-butyl mandelate (2b) with appreciable enantioselectivities, respectively.