Nearly monodisperse polystyrene nanospheres coated with platinum have been synthesized and applied successfully in the cinchona alkaloid-modified enantioselective hydrogenation of ethyl pyruvate. During the catalyst preparation broadly varied experimental conditions were used resulting in several catalysts with different properties. The effect of hydrogen pressure, solvent, modifier and polystyrene nanoparticle size on the enantioselectivity was also studied. Based on the results the effect of support on the mechanism of the enantiodifferentiation has been discussed.