The structural, morphological and photoelectrochemical features of coherent CdSe and CdSexTe1−x thin film semiconductors, prepared by cathodic electrodeposition from an acid sulfate solution, were investigated. In particular, the effect of deposition potential on the properties of layers grown onto Ti and Ni substrates, in connection with the electrolyte acidity within the bath pH interval [2.2, 1.6], was studied. As verified by X-ray diffraction (XRD), scanning electron microscopy (SEM), reflectance and photoelectrochemical cell (PEC) tests, the preparation method renders compact semiconductive films, presenting a remarkably intense in the case of CdSe/Ni(111) cubic structure, without any post-thermal treatment. The passive surface of Ti is associated with weaker texture; however, deposits on Ti generally exhibit better photoelectrochemical behavior, under similar preparation conditions.