Preformed aliphatic polyesters bearing pendent acrylate groups, poly(4-acryloyloxy-epsilon-caprolactone)co-epsilon-caprolactone) [poly(ACL-co-epsilonCL)], were grafted onto metallic surfaces by a cathodic electrochemical process. Content of acrylates must exceed a lower limit for them to be adsorbed on the cathode with the proper orientation and for the grafting to be successful. The strongly adhering films were analyzed by IR reflection-absorption spectroscopy and scanning electron microscopy. As a result of the known miscibility of poly-e-caprolactone with poly(vinyl chloride) (PVC), the pregrafting of poly(ACL-co-epsilonCL) imparts strong adhesion to PVC topcoats.