The results of an investigation on catalytic systems arising from the electrochemical activation of salts and complexes of several transition metals for the carbonylation of methanol to dimethylcarbonate (DMC) are reported. Metals were tested as inorganic salts or complexes with ligands such as 2,2’-bipyridine (bipy), 1,6-bis (2-oxyphenyl)-2,5-diaza-1,5-hexadiene (salen), 2,4-pentanedionate (acac), triphenylphosphine (TPP) in methanol at room temperature saturated with carbon monoxide at atmospheric pressure. Best faradic yields vs DMC were observed as follows : CuCl(bipy) : 84.8%; PdCl2(bipy) : 64.0%; CoCl2 : 26.0%; RhCl3 : 25.0%; AgBF4(bipy) : 10.2%; AuCl3 : 9.4%; Cr(acac)(3) : 6.7%; PtCl2(bipy) : 2.1%; NiCl2 : 1.8%. The influence of the ligand on faradic yields has been also investigated.