A novel two-step approach for the cathodic electrodeposition of CdTe films, based on the initial electrochemical modification of poly-crystalline gold substrates with elemental tellurium, is described. This Te-modified An electrode is subjected to electroreduction (to generate Te2- species) in a separate, Te-free medium containing Cd2+ species. In situ precipitation results in the formation of a CdTe semiconductor film. For this two-step approach to work, the electroreduction of Cd2+ species will have to be shifted to more negative potentials past the Te-0 -> Te2- conversion regime. This was accomplished in the present study by complexation of Cd2+ species with ethylenediaminetetraacetic acid (EDTA). The CdTe films thus obtained were characterized by linear sweep voltammetry, electrochemical quartz crystal microgravimetry, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, and photoelectrochernical experiments. (c) 2006 Elsevier B.V. All rights reserved.