The feasibility of the enantioselective electroreduction of pro-chiral acetophenone was investigated at the silver cathode in an undivided cell for the first time. Electroreduction of acetophenone in the presence of cinchonidine (CD) yielded two main products: the optically active alcohol, and the dimer product pinacol with no optical rotation. The influence of water in the co-solvent (MeCN/H2O), supporting electrolyte, electrode material, current density, and the alkaloid type on the enantiomeric excesses (ee) and yield was investigated. Under the optimized conditions, the alcohol was obtained with a 21.6% ee and a 3.6% yield, whereas, an 83.2% yield and a 5.5 dl/meso ratio were obtained for pinacol. The electrochemical behavior of the samples was also studied through cyclic voltammetry (CV). Finally, we proposed a possible induction mechanism based on the results of the electrolysis and CV. (C) 2013 Elsevier Ltd. All rights reserved.