The cathodic behaviour of silver in 0.01 M NaCl and 0.01 M NaCl + 1.0 alcohols which are methyl, ethyl and propyl alcohols is investigated at pH 3 and 5 by means of electrolysis. The experimental (E-exp) and theoretical (E-rev) discharge potential are determined in all solutions between Pt and Ag electrodes. The cathodic and anodic overpotentials on silver cathode were determined using a platinum anode. The hydrogen gas is produced on constant potentials (5.00 or 10.00 V) on silver cathode. It is observed that the presence of alcohols decreases the anodic overpotential and increases the hydrogen yield in NaCl solution. (C) 2003 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.