The paper describes hydrogenation of unsaturated alcohols, alkenes and dienes in individual and binary systems of substrates by use of catalytic hydrogen transfer from ammonium formate in methanol on a palladium catalyst. A significant structural effect of hydrogenated alcohols upon their reactivity and adsorptivity was observed, Following comparison to the data acquired from typical hydrogenation by use of molecular hydrogen, it was inferred that the components of the CTH system increase the selectivity of competitive transfer hydrogenation to a significant extent in systems of unsaturated alcohol - unsaturated hydrocarbon with regard to the relative increase of reactivity of unsaturated alcohols, This occurs primarily due to affecting the relative adsorptivity.