Epitaxial growth of cadmium sulfide on InP 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 InP and CBD-CdS. Direct relations between the substrate properties and the growth habits of the CdS film (hexagonal vs. cubic, epitaxial vs. polycrystalline) are found.