The electrochemical stability of 10 organic cations, which can be used in ionic liquids (IL), was investigated as solutes in acetonitrile (ACN). The stability of three of the salts, BenMe(2)EtNCl (salt III), 1-butyl-2-methyl pyrrolidium chloride (salt VI), and its structural isomer, BuMe(2)ProNCl (salt VII), were also compared in chloroaluminate ILs. The chloroaluminate ILs of salts VI and VII are investigated for the first time. The NaCl-neutralized ILs of salts VI and VII have melting points of 43.2 and 3.7 degrees C, respectively. The benzyl-substituted cation, salt III, was more easily reduced in ACN or as the neutral chloroaluminate IL than the alkyl-substituted cation, salt VII, due to the better leaving ability of the benzyl group. Mass spectroscopy measurements before and after electrolysis on the benzyl-substituted solutions confirmed that reduction involves the loss of an alkyl group. In ACN, salt VI was found to be the most difficult to reduce (1 mA/cm(2) at -2.09 V) due to its cyclic structure. However, in the chloroaluminate IL, the pyrrolidinium cation was more easily reduced than salt III or its isomer, salt VII, resulting in an insoluble black deposit. This is consistent with the mass spectrometry data, which do not show formation of low-molecular-weight products, as in the reduction of salts III and VII. The IL of salt VII was the most stable in the presence of sodium. Sodium ions could be reduced and reoxidized with a maximum Coulombic efficiency of 94.1% versus 87.2% for salt VI. Reduction of the pyrrolidinium cation produces insoluble products, most likely through opening of the cyclic ring, and an inferior medium for sodium ion reduction compared to the benzyl- and butyl-substituted cations, even though reduction of the cation occurs at a more negative potential in acetonitrile.