Hydrogenation of acetophenone and esters of ketoacids with molecular hydrogen in the presence of the Pd(acac)2–(–)-cinchonidine–H2 catalytic system has been studied. The dependence of the molar ratio of (–)-cinchonidine/Pd on size and shape of palladium nanoparticles, formed in the system, also on reaction rate and enantioselectivity has been established. The nature of the regularities observed for the Pd(acac)2–(–)-cinchonidine–H2 catalytic system was discussed.