Adventitious water is often the main protonating agent towards the basic intermediates of organic electrode reductions in dipolar non-protogenic solvents. OH- ions thus formed do not generally modify the reduction pattern, unless they are able to catalyze the transformation of some of the species involved in the electrode process. This is the case in the two-electron reduction of Ph(3)CSC(6)H(4)CN in DMF, which involves proton transfer from residual water to the reduction intermediate Ph(3)C(-). The ensuing OH- ions catalyze hydrolysis of the substrate, with formation of the corresponding amide. The hydrolysis process is sufficiently fast to show its effect not only during macroscale electrolysis but also in the much shorter time scale of low sweep rate cyclic voltammetry. However, the reaction can easily be hampered by addition of even mild proton donors, thus causing only minor perturbations in the reaction medium.