This research investigates the optical, structural, electrical, and photoelectrochemical characteristics of CdS/CdSe heterojunctions formed on both ITO and p–Si substrates. The deposition of CdS and CdSe films was carried out using the chemical bath deposition method, which is economical and simple method. The optical, structural, and electrical properties of CdS/CdSe heterojunctions were analyzed through UV–Vis spectrometry, photoluminescence (PL) spectroscopy, field emission–scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), Raman spectroscopy, and Hall‐effect measurements. Furthermore, Mott–Schottky analysis was employed to investigate the electrochemical properties of the semiconductor CdS/CdSe heterojunctions on both ITO and p–Si substrates. Additionally, the photoelectrochemical investigations of CdS/CdSe heterojunctions on ITO and p–Si substrates were conducted by electrochemical analyses using linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and photocurrent – time plots under both dark and illuminated conditions.