Epitaxial growth of cadmium sulfide on single crystals is achieved by chemical bath deposition (CBD) in ammonia solutions at near room temperature. A better understanding of the correlations between the deposition parameters (temperature, bath composition) and the epitaxial quality is obtained by using electron diffraction and transmission techniques, x‐ray diffraction, in combination with Raman spectroscopy. They are supplemented by electrochemical impedance and photocurrent experiments which give information on energetic structures between and . Direct relations between the substrate properties and the growth habits of the film (hexagonal vs. cubic, epitaxial vs. polycrystalline) are found.