New ruthenium(II) complexes containing one or two pyrrole-functionalized polypyridylic ligands have been prepared in order to study their electrochemical behaviour in heterogeneous phase, after anodic polymerization from CH2Cl2 solution on an electrode surface. Complexes containing one pyrrole unit have general formula [Ru(bpea-pyr)(bpy)(L)](2+) (bpea-pyr = N-[3-bis(2-pyridylmethyl)aminopropyl]pyrrole, bpy = 2,2'-bipyridine, L = Cl, complex 3, or L = H2O, complex 1), whereas compounds having two pyrrole units correspond to [Ru(bpea-pyr)(bpy-pyr)(L)](2+) (bpy-pyr = 4-methyl-4'-pyrrolylbutyl-2,2'-bipyridine, L = Cl, complex 4, or L = H2O, complex 2). Upon oxidative polymerization, all complexes form highly stable polypyrrolic films on a graphite disk electrode surface. An electrode modified with complex 2 polypyrrole coating film, C/poly-2, has been tested as heterogeneous catalyst for the oxidation of benzyl alcohol, showing a remarkably high efficiency and notably improving the results obtained with analogous complexes in homogeneous phase. (C) 2003 Elsevier Science Ltd. All rights reserved.