Fe2O3/ZnO heterojunction has attracted great attention due to the possibility of overcoming low Photoelectrochemical (PEC) cell efficiency the limitation of a single layer of semiconductor electrodes. The aim of this study is to investigate the effect of Fe2O3, ZnO and Fe2O3/ZnO films on PEC efficiency. The Fe2O3, ZnO and Fe2O3/ZnO films were fabricated by spin coating and doctor blade methods, respectively. All the films were characterized by XRD, SEM, and Cyclic Voltammetry (CV). Based on structural results, Fe2O3 and ZnO nanoparticles can grow well on the ITO substrate and they exhibit trigonal and hexagonal crystal structures, respectively. Moreover, we found that the PEC efficiency increases after ZnO are coated on Fe2O3 film. The combination of Fe2O3 and ZnO can effectively increase the separation of electrons and holes that can improve the photocatalytic activity of PEC cells based on the structural coordinates of their energy levels. © 2020 American Institute of Physics Inc.. All rights reserved.