The redox chemistry of Ce(III)DOTA in cage in carbonate solutions was studied using electrochemistry and radiolysis techniques (continuous radiolysis and pulse radiolysis). Spectroscopic measurements point out that the species present in the solutions at high bicarbonate concentrations are [Ce(III)DOTA(CO3)](3-) (or less plausible [Ce(III)DOTA(HCO3)](2-)) with the carbonate (bicarbonate) anion as the ninth ligand versus [Ce(III)DOTA(H2O)] - present in the absence of bicarbonate. Electrochemical results show a relatively low increase in the thermodynamic stabilization of the redox couple Ce-IV/III in the presence of carbonate versus its aqueous analogue. [Ce(IV)DOTA(CO3)](2-) and [Ce(IV)DOTA(H2O)], prepared electrochemically, decompose photolytically. However, kept in the dark, both are relatively long lived; [Ce(IV)DOTA(H2O)], though, is orders of magnitude kinetically more stable (a considerably longer half-life). Thus, one concludes that the carbonate species have a different mechanism of decomposition depending also on the presence of dioxygen after its preparation (in deaerated/aerated solutions). The [Ce(IV)DOTA(CO3)](2-) species is produced . radiolytically by oxidation of the trivalent species by CO3 center dot- with a rate constant, measured using pulse radiolysis, of 3.3 x 10(5) M-1 s(-1). This rate constant is at least 1 order of magnitude smaller than most of the rate constants so far reported for the reaction of CO3 center dot- with transition metal/lanthanide (cerium)/actinide complexes. This result together with the bulkiness of the reactants might suggest an outer-sphere electron transfer rather than the inner-sphere one so far proposed. The lifetime of the tetravalent cerium species obtained radiolytically in the presence of carbonate is shorter than the electrochemical on; suggesting a different conformer involved.