An electrochemical deposition process of ZnSe and CdSe compound semiconductors from aqueous acidic solutions onto silicon substrates with porous silicon layers formed on their surfaces was studied by the voltammetry method. The experimental data obtained were compared with the deposition data onto metal and silicon substrates, and the optimal conditions for the binary compound deposition onto porous silicon were determined. Semiconductor films deposited were studied by scanning electron microscopy. X-ray diffractometry, and X-ray microanalysis. The films are shown to have the crystalline structure and a nearly stoichiometric composition with a minor Se excess. Further annealing in air for 15 min allowed the Se concentration to be decreased. (C) 2009 Elsevier B.V. All rights reserved.