The adoption of suitable experimental conditions, which comprise ultra-dry solvents and electrolytes with very high oxidation resistance and low nucleophilicity, has allowed observation, for the first time, of the cyclic voltammetric reversible generation of C602+ and C603+. The present study adds valuable information on the still relatively unknown properties of these important all-carbon carbocations and, in view of their very high reactivity, offers new possible routes for fullerene functionalization.