CdS-CuS heterojunction films have been grown successfully on a copper substrate using a chemical bath deposition (CBD) method. The obtained films are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), optical absorption, Raman spectroscopy and photoluminescence (PL) analysis and the photo-electrochemical (PEC) properties of the CdS-CuS heterojunction have been studied using different electrolytes. The XRD pattern of CuS-CdS shows peaks corresponding to CuS (hexagonal) and CdS (cubic) structures, while the optical absorption studies revealed the presence of an absorption edge corresponding to CuS-CdS (band gap of 1.85 eV). The Raman spectra of the CuS, CdS and CuS-CdS heterojunctions were recorded and are in good agreement with the results reported in the literature. TEM and cross-sectional SEM images show an overlap between CuS rods and CdS flasks. The charge transfer across the layers was studied by using PL spectra. The measurement of the photo-electrochemical properties using a conventional two electrode system for an iodine electrolyte showed the highest conversion efficiency of 1.40% as against for potassium ferro-ferricyanide (0.38%) and polysulphide electrolytes (0.02%).