The preliminary results on the electrochemical activation of catalytic systems based on copper and cobalt complexes for the carbonylation of methanol to dimethylcarbonate at room temperature and atmospheric pressure are reported. Faradic yields up to 70%, with very high selectivity towards dimethylcarbonate, were observed with CuCl(2,2’-bipyridine). Positive results were also obtained, although with poorer catalytic activity, with other complexes such as CuCl(tetramethylethylenediamine), [Co(1,6-bis(2-oxyphenyl)-2,5-diaza-1,5-hexadiene)]0.5 H2O and Co(2,4-pentanedionate)(2).