The electrochemical reduction of carbonyl-containing methanofullerenes is studied by methods of cyclic voltammetry and ESR with in situ electrolysis in the environment of 0.1 M Bu4NBF4 in o-dichlorobenzene-dimethylformamide (3:1 by volume). It is shown that the one-electron transfer onto the fullerene sphere of these compounds induces opening of the three-membered cycle, which leads to processes of retrocyclopropanation, transfer of the adduct onto the fullerene sphere of another molecule with the formation of bismethanofullerenes, and transformation into fullerodihydrofuran. The totality of competitive processes and the balance between these is defined by the nature of substituents at the exocarbon atom and the experimental conditions. The opening process is interpreted as the intramolecular electron transfer from the fullerene sphere onto the three-membered cycle.