The selectivity of the electrocatalytic hydrogenation (ECH) method for the reduction of nitro compounds to the corresponding amines is compared with that of reduction by Raney copper (RCu) alloy powder in alkaline aqueous ethanol. In the former method, chemisorbed hydrogen is generated in situ by electrochemical reduction of water. In the latter method (termed "chemical catalytic hydrogenation" (CCH)), chemisorbed hydrogen is also generated in situ but by reduction of water by aluminium (by leaching of the alloy). Finally, the selectivity and efficiency of the electrochemical reduction of 5-nitro-indoles, -benzofurane, and -benzothiophene at RCu electrodes in neutral and alkaline aqueous ethanol is compared with that of the classical reduction with zinc in acidic medium.