This work reports results achieved when a specially designed monomer, the allyl ether of p-benzenesulphonic acid, with a pendent anionic group, was used to prepare a polymeric matrix. Ion exchange with cupric ions followed by electrochemical reduction provided polymer films with highly dispersed Cu-0 particles. Immersion of the copper bearing modified electrode in a PdCl4 (2-) containing solution produced a displacement reaction causing the deposition of 50-200 nm sized Pd particles. The presence of Pd particles in the so-prepared films was confirmed by voltammetry, SEM/EDS and XRD. The behaviour of the submicron Pd particle/poly(allylbenzene p-sulphonic acid) modified electrode towards the HER was evaluated by recording polarization curves. The electrocatalytic activity reveals that the methodology is a promising approach for the preparation of cathodes for the electrohydrogenation of organic molecules.