In this work, the CuO nano-powder has been synthesized by employing chemical bath deposition technique for its subsequent use to grow ultrathin film (20 nm) of p-CuO on n-Si substrate for the fabrication of p-CuO/n-Si hetero-junction diodes. The thin CuO film has been grown by employing vapour-liquid-solid method. The crystalline structure and chemical phase of the film are characterized by employing field-emission scanning electron microscopy and X-ray diffraction studies. Chemical stoichiometry of the film has been confirmed by using energy dispersive X-ray spectroscopy. The potential for photovoltaic applications of such films is investigated by measuring the junction current-voltage characteristics and by extracting the relevant parameters such as open circuit photo-generated voltage, short circuit current density, fill-factor and energy conversion efficiency. © 2016 Elsevier B.V.