Four fullerene derivatives have been synthesized and analyzed using electrochemical techniques at low temperatures and at very negative potentials. Two of these systems are diphenyl methanofullerene derivatives, 1 and 2, while the others are [4+2] cycloaddition products containing a benzocrown group attached to the resulting cyclohexenyl adduct, structures 3 and 4. For all four cases, it is possible to observe at least four successive, regularly spaced, chemically and electrochemically reversible waves using cyclic voltammetry. The potential values for these first four waves differ slightly from one compound to the other, reflecting the expected differences in electronic properties of the attached groups. While 1 exhibits potential values that are very similar to those of C-60, all other derivatives show waves that are cathodically shifted. In terms of increasing cathodic potential values, the compounds follow the order C-60 congruent to 1 less than or equal to 2 less than or equal to 3 less than or equal to 4. For the first time for any fullerene derivatives, reduction waves beyond the fourth one have been observed for these systems. Interestingly, one of the methanofullerene adducts, 1, and one of the [4+2] cycloaddition products, 3, exhibit what appears to be a larger than expected potential gap between the fourth and the next observable reduction wave at room temperature. Either by scanning the potential faster or by lowering the temperature, it was possible to observe an additional redox couple for 1 immediately following the fourth reduction at the expected potential. The same was not true for 3. Both 2 and 4 exhibit similar voltammetric behavior, which is different from that of 1 and 3 and more in-line with anticipated results, since they exhibit regularly spaced reduction waves, down to the fifth reduction. Compound 4 does not exhibit temperature or scan rate changes of its voltammetric response, while 2 does to some extent. Results are interpreted in terms of homogeneous chemical processes following the electrochemical formation of the tetraanions of 1, 2, and 3, leading to the formation of phenyl-stabilized carbanionic intermediates. In the case of 1 and 2, another homogeneous chemical process is observed, which is tentatively attributed to an electrochemically induced methanofullerene-fulleroid reaction involving a dinorcaradiene-[10]annulene type equilibrium.