Most physical deposition methods are unable to cover the inner surface of porous silicon (PS), whereas electroplating has been successfully used. So it seems very attractive to use the electrochemical deposition of a semiconductor such as CdTe to create a nanocomposite structure and to provide charge injection into the structure. We show that CdTe can be deposited on silicon and porous silicon from an electrolyte containing CdSO4 and TeO2 in acidic conditions. Physical analysis by X-ray diffraction, X-ray photoelectron spectroscopy and Auger electron spectroscopy confirm that the deposits are microcrystalline CdTe showing a preferential orientation along the (111) direction. Afterdeposition, the photoluminescence intensity of porous silicon is found to be strongly affected, particularly upon drying.