We report a facile synthesis of ZnO/Fe2O3 heterostructures based on the hydrolysis of FeCl3 in the presence of ZnO nanoparticles. The material structure, composition, and its optical properties have been examined by means of transmission electron microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and diffuse reflectance UV-visible spectroscopy. Results obtained show that 2.9 nm-sized Fe2O3 nanoparticles produced assemble with ZnO to form ZnO/Fe2O3 heterostructures. We have evaluated the photodegradation performances of ZnO/Fe2O3 materials using salicylic acid under UV-light. ZnO/Fe2O3 heterostructures exhibited enhanced photocatalytic capabilities than commercial ZnO due to the effective electron/hole separation at the interfaces of ZnO/Fe2O3 allowing the enhanced hydroxyl and superoxide radicals production from the heterostructure.