Bimetallic Pd-Cu-composites of polyaniline prepared by introducing metals (II) chlorides in the process of oxida-tive polymerization of aniline with and without chemical reduction by sodium borohydride are applied to copper cath-ode activation in electrohydrogenation of phenylacetylene in basic aqueous ethanolic solutions of catholyte. Electro-catalytic activity of composites that they exhibited in the process is due to formation of metal particles (and their al-loys) by electrochemical reduction of metal cations in the polymer matrix. The main hydrogenation products are ethyl benzene and 1,4-diphenylbutane, the yields of which influence metal content in the studied composites.