Dithiocarbamate (dtc) complexes of chromium(III) containing oxygen-expanded ligands, odtc, can be synthesized. With pyrrolidine-TV-carbodithioate ([pdtc]-) as the dithiocarbamate ligand, the electrochemistry of both Cr(pdtc)3 and Cr(pdtc)2(opdtc) has been examined in detail. On the basis of studies employing cyclic and differential-pulse voltammetry at platinum, gold, and glassy-carbon electrodes in methanol, acetone, acetonitrile, and dichloromethane, it has been shown that the formally chromium(IV) complex, [Cr(pdtc)2(opdtc)]+, is kinetically more stable than [Cr(pdtc)3]+. Thermodynamically, the same stability order also applies in the sense that Cr(pdtc)2(opdtc) is easier to oxidize than Cr(pdtc)3. The enhanced stability is attributed to the increased importance of the resonance form.