Heterostructured Fe3O4/ZnO films were fabricated by an aqueous solution process named the spin-spray method at a low substrate temperature of 95 °C. The surface morphology of the ZnO single layer changed from rod array to dense structure by adding citrate ions in the reaction solution. It indicated high optical transmittance above 85%, and exhibited a low electrical resistivity in the range of $\sim 10^{\mathrm {-2}}~\Omega \cdot \text {cm}$ after UV irradiation. In case of the Fe3O4 single layer, it had magnetite phase and another impurity peak was not observed. Then, Fe3O4 layer was deposited successively on the ZnO layer, and the as-fabricated Fe3O4/ZnO film had a preferential orientation along (nnn) plane, while other peaks identified for Fe3O4 were also detected. Scanning electron microscopy images of the as-fabricated Fe3O4/ZnO films indicated a cubic shape.