Good stoichiometry of cadmium sulfide (CdS) film facilitates its application in photovoltaic devices; however, traditional thermal evaporation usually results in a Cd-deficient CdS film at a low-substrate temperature. In this study, Cd-rich CdS quantum dots (QDs) were synthesized by a facile co-precipitation method and used as the precursor to thermally evaporate CdS film on indium tin oxide-coated glass (ITO/glass). As a consequence, the stoichiometry of CdS film was greatly improved with atomic ratio of Cd to S restored to unity. More importantly, the newly developed CdS film, with its rod-like surface microstructure, acted as an efficient photoanode in a photoelectrochemical (PEC) cell. Its properties, including surface morphology and roughness, crystal structure, chemical composition, film thickness, energy-level structure and photosensitivity, are studied in detail.