Electroreduction of 4-amino-6-methyl-3-thio-1,2,4-triazine-5-one (1), 6-methyl-3-thio-1,2,4-triazine-5-one (II), and 2,4-dimethoxy-6-methyl-1,3,5-triazine (III) in dimethylformamide was investigated. Electrochemical techniques including differential pulse voltammetry (DPV), cyclic voltammetry (CV), chronoamperometry, and coulometry were employed to study the mechanism of the electrode process. From the analysis of the voltammetric and spectroscopic experiments a mechanism was proposed for the electroreduction of thio-triazine and triazine compounds. Compounds I and II having thiol groups exhibited similar redox behavior. Both compounds displayed two cathodic peaks, whereas the third compound (III), with no thiol group, showed only one cathodic peak in the same potential range as the second peak of compounds I and II. The results of this study show that in the former wave, the one electron reduction of thiol led to a dimer (disulfide) species and in the latter, the triazine ring was reduced in a two-electron process. The effects of various physical and electrochemical parameters were studied and the electrochemical behavior of the monomers was reported as a function of these parameters. A completely irreversible behavior was observed from cyclic voltammograms obtained under different conditions. Furthermore, in this study some numerical constants, such as diffusion constant, transfer coefficient, and rate constant of coupled chemical reaction were determined. (c) 2005 Elsevier B.V. All rights reserved.