Abstract The electrochemical reduction of some N-acylamino-, N-amino-, N-benzyl-and N- phenacyl-substituted pyridinium and triazolium ions is investigated in acetonitrile by voltammetric methods and potentiostatic electrolyses. The acylaminopyridinium ions 1 and the arylaminopyridinium ions 3 are cathodically cleaved into the pyridine derivative and the carboxylic amide or the aromatic amine. In the case of the 1-benzyl-4-acylaminotriazolium ...