A regioselective alkoxycarbonylation of imidazoheterocycles using carbazates as ester group sources in DMSO was developed, in which an inexpensive FeCl2·4H2O was used as the catalyst and (NH4)2S2O8 was the oxidant. The reaction proceeded smoothly under an air atmosphere to give the 3-alkoxycarbonylated products in moderate to good yields.