The reduction of microcrystalline C 60 fullerene, adhered at a carbon electrode and immersed in aqueous electrolyte, has been studied under various voltammetric conditions. This work reports mainly the voltammetric studies carried out principally in electrolyte containing potassium ions. Comparison of adherence techniques, such as solvent casting and mechanical transfer methods, are made to assess if the type of adhered techniques has any significant influence on the observed electrochemistry. The solvent casting method is found to produce three peaks in the potential for C 60 0/n- in the presence of K 60 is compared with other cations, such as Li, Na, Rb and Cs, it is observed that the shift of reduction potential follows the change in the hydration energy in the order Cs>Rb>K>Na>Li. In a mixed electrolyte study of CsCl/KCl, the reduction potential and peak shape of C + is compared with other cations, such as Li, Na, Rb and Cs, it is observed that the shift of reduction potential follows the change in the hydration energy in the order Cs>Rb>K>Na>Li. In a mixed electrolyte study of CsCl/KCl, the reduction potential and peak shape of C 60 is irreversible in aqueous electrolyte containing alkaline cations as the re-oxidation process does not produce any observed electro-activity. Evidence of the formation of a passive coating of K 0/n-redox couple during cyclic voltammetry is observed to change with concentration of the cations and the observed electrochemistry can be attributed to a cation-exchange mechanism. The reduction of C 60 is irreversible in aqueous electrolyte containing alkaline cations as the re-oxidation process does not produce any observed electro-activity. Evidence of the formation of a passive coating of K nC 60 fulleride, which does not appear to undergo dissolution is obtained under cyclic voltametric conditions. This coating remains electrochemically active in the presence of tetrabutylammonium ions in acetonitrile. Scan rate, chronocoulometric, and scanning electron microscopic studies provide evidence of the presence of a surface process involving solid–solid transformation. [ABSTRACT FROM AUTHOR]