This paper reports on the preparation of polyester brushes at the surface of electrically conducting materials. A two-step strategy has been worked out that consists of the electropolymerization of an acrylate under a cathodic potential, such that the polyacrylate layer is chemisorbed at the surface. In a second step, either preformed poly(epsilon-caprolactone) chains are grafted onto the polyacrylate sublayer or the ring-opening polymerization of epsilon-caprolactone is initiated from it.