The electrochemical behavior and complex structure of Np carbonato complexes, which are of major concern for the geological disposal of radioactive wastes, have been investigated in aqueous Na2CO3 and Na2CO3/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 15 M Na2CO3 with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex. [NpO2(CO3)(3)](n-) (n=5 for Np-V, and 4 for Np-VI). Hence, the electrochemical reaction of the Np-V/VI redox couple merely results in the shortening/lengthening of bond distances mainly because of the change of the cationic charge of Np, without any structural rearrangement. This explains the observed reversible-like feature on their cyclic voltammograms. In contrast, the electrochemical oxidation of Np-V in a highly basic carbonate solution of 2.0 M Na2CO3/1.0 M NaOH (pH > 13) yielded a stable heptavalent Np complex of [(NpO4)-O-VII(OH)(2)](3-), indicating that the oxidation reaction from Np-V to Np-VII in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO32-) to hydroxide ions (OH-).