Enantioselective hydrogenation has been reviewed from the standpoint of the chemistry of the metallic active phase. A comparative study is presented of the behaviour of the platinum group metals as catalysts for pyruvate ester hydrogenation, and this is extended to embrace the hydrogenation of other functions as far as the literature permits. Attention is drawn to the operation of thermodynamic and kinetic factors in the determination of enantioselectivity, to the molecular complexities of the adlayer in which enantioselection is achieved, and to approaches that might be made to advance our understanding of these systems.