Cadmium telluride thin films were fabricated on Ti and Nesatron® substrates by electrodeposition and characterized by x‐ray diffraction, scanning electron microscopy, energy dispersive x‐ray analyses (EDAX), optical transmission measurements, and photoelectrochemical (PEC) studies. The deposition‐bath preparation procedure was slightly modified from the literature method to permit initial speciation of and thereby increase the loading level of Te in the film. New data are presented on the electrochemistry of the deposition process and on the cyclic voltammetric behavior of containing electrolytes in the pH range from ∼0.7 to 11.0. The films after suitable annealing in an Ar atmosphere show x‐ray diffraction behavior consistent with a hexagonal structure. Data from EDAX show that the Cd/Te ratio in the film is sensitive to the annealing process. Concomitantly, the conductivity also changes from p‐type to n‐type, as shown by PEC measurements on the films containing a protective coating in contact with alkaline polysulfide electrolytes. Finally, some preliminary data are presented on PEC cells based on these thin films in a nonaqueous electrolyte system comprising the ferrocene/ferricenium ion redox couple.