The electrooxidation of azaferrocene (AF) and 2,5-dimethylazaferrocene (DMAF) has been investigated in several solvents and under various conditions of basicity and nucleophilicity, by cyclic voltammetry at scan rates ranging between 1 and 500 V s(-1). The kinetics of the AF(+) cation decomposition have been found to be first order (vs. the substrate), and strongly dependent on both the solvent and the possible presence of a base. The results tend to demonstrate that the decomposition of AF(+) cations is more probably associated with a deprotonation reaction than with a nucleophilic attack.