A new enantioselective heterogeneous catalytic system has been made by partly decomposing (hydrogenolyzing) chiral silyl ethers in hydrogen over Pd black and differently dispersed Pd/SiO2. Preliminary hydrogenations of two prochiral C=C’s have demonstrated the feasibility of the method which produced catalysts attaining ee’s up to 22%. The chiral silyl ethers appear to hydrolyze off the surface, but in the absence of water, the new catalysts catalyze reproducible ee’s.