Hexanitro-fullerene was synthesized. Hexahydroxy-fullerene was obtained by hydrolysis of the resulting hexanitro-fullerene in situ. The electrochemical properties have been investigated by using cyclic voltammetry and controlled potential electrolysis technique. Two reduction peaks of C60(OH)6 with quasi-reversibility in DMF solution were observed. No electrochemical response was observed for the C60(OH)12 compound in a variety of solvent. An electrode following chemical reaction occurred for C60(NO2)6 after the first reduction at − 0.96 V. The trace amount residue of C60(NO2)6 shows quasi-reversible redox behavior. The results from the controlled potential electrolysis show that the C60(NO2)6 has six sequential electron transfer at − 0.96 V (vs. Fc/Fc+) to produce free C60 and NO2− anion.