The ability of [(eta(5)-Me5C5)M(L)Cl](+) (L = 2,2’-bipyridine ligands; M = Rh(III) and Lr(III)) to act as an electrocatalyst for CO, reduction has been examined in an aqueous organic medium. It appears that the Rh(III) complex is a better catalyst than the Ir(III) one, and that a current efficiency for formate production of up to 50% can be reached. The initial step of the electrocatalysis involves the formation of the corresponding hydride complex. Immobilization of such catalysts on the electrode surface, by the technique of functionalized polypyrrole films, decreases their efficiency as a consequence of the lower efficiency of the insertion of CO2 into the metal-hydride bond.