The anodic oxidation of 1-naphthylamine (ArNH,) has been studied at the platinum and vitreous carbon electrodes in methylene chloride (MC) by cyclic voltammetry and controlled-potential electrolysis. These studies confirm previous work in other solvents, but, because of the fact that MC allowed us to work up to -7O"C, the temperature effects on product distribution could be analysed. Some aspects of the mechanism previously proposed have also been confirmed. The electrooxidation of ArNH, in MC gives only two dimeric products, ie l,l'-naphthidine (0,) and 4amino-l,l'-dinaphthylamine (D,,) whose yield are highly dependent on the temperature. Thus at temperatures higher than 20°C practically only D,, is detected while at temgerature of -60°C is D, predominant. Two competitive processes for the dimerization of the ArNH;' produced in the first charge transfer step are proposed. The inverse effect on temperature observed for the formation of D, is explained considering a previous equilibrium to dimerization, which involves a charge transfer complex between two ArNH; ' species. On the other hand D,, formation is proposed through dimerization of ArNH' following deprotonation of cation radical. A semiquantitative method to be applied to cyclic voltammograms and based on the kinetic expression is proposed to determine the selectivities of the competitive processes.