In the cathodic reduction of acetophenone to 1-phenylethanol and 2,3-diphenyl-2,3-butanediol in aqueous media, the effects of electrolytic conditions such as electrode materials, supporting electrolyte, electrode potential and additives were systematically studied. When the controlled-potential electrolysis of acetophenone was performed at -2.1 V versus SCE on a Pb plate cathode in water containing both sodium sulfate and cationic surfactants such as cetyltrimethylammonium bromide (CTAB), 1-phenylethanol was selectively formed with current efficiencies of 67-94%. The mechanism for the role of cationic surfactants was discussed.