Cadmium oxide (CdO) thin films were synthesized by the sol–gel method. The films were analyzed by means of XRD, AFM, and UV/Vis spectrophotometry. X-ray diffraction patterns confirm that the films are formed from CdO with cubic crystal structure and consist of nano-particles. The energy gap of the prepared film was found to be 2.29 eV. The current–voltage (I–V) characteristics of the CdO/p-Si heterojunction were examined in the dark and under different illumination intensities. The heterojunction showed high rectifying behavior and a strong photoresponse. Main electrical parameters of the photodiode such as series and shunt resistances (R s and R sh), saturation current I 0, and photocurrent I ph, were extracted considering a single diode equivalent circuit of a photovoltaic cell. Results indicate that the application of CdO thin films as an electron transport layer on p-Si acts as a photodetector in the field of the UV/visible.