New cis-diaquo ruthenium(II) complexes [Ru(L)(2)(OH2)(2)](2+) with L = 2,2’-bipyridine substituted by ramified or long chain alkyl groups have been prepared in order to study their electrochemical behaviour in a non-coordinating solvent like CH2Cl2. Slow mono and bis-aquo substitutions by counter anions (Y-) from the electrolyte are observed leading to [Ru(L)(2)(OH2)(Y)](+) and [Ru(L)(2)(Y)(2)]. The kinetic of the process is time dependent on the electrolyte used (TBAP or TBATF). By using a 2,2’-bipyridine ligand functionalized by a pyrrole group (L(1)), films of poly[Ru(L(1))(2)(OH2)(2)](2+), poly[Ru(L(1))(2)(OH2)(Y)](+) and poly[Ru(L(1))(2)(Y)(2)] are readily obtained by anodic polymerization. These modified electrodes were electrochemically and spectrochemically characterized and the electrocatalytical properties of the C/poly[Ru(L(1))(2)(OH2)(2)](2+) modified electrode have been examined.