The problem of water pollution has become an urgent global issue. As one approach for addressing this problem, in this work, rod-like ZnO nanostructures were synthesized by a simple electrodeposition method, which can purify wastewater by photocatalytic reaction. ZnO was deposited on indium tin oxide (ITO) conductive glass by electrodeposition, and then the surface of the sample was modified by 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane to make the surface super-hydrophobic. ZnO nanorods with a “photocatalytic and self-cleaning” synergistic effect were obtained. The morphology and structure of the samples were analyzed by field emission scanning electron microscopy (FESEM) and x-ray diffraction (XRD). FESEM images show that different deposition times, water bath temperatures, electrolysis times, and electrodeposition voltages have different effects on the surface morphology of the materials. XRD patterns show that the crystal structure of nano-ZnO is a hexagonal wurtzite crystalline structure. The optical properties of the samples were characterized by UV–Vis spectrophotometry. The hydrophobicity of the materials was characterized using a droplet shape analyzer. Photocatalysis results show that the modification can improve the photocatalytic efficiency of the materials. The results show that the material has excellent optical properties, and because of its super-hydrophobicity, there are no residual small particles on the surface after the photocatalytic reaction. Therefore, this material not only has high photocatalytic performance, but can also be recycled for treatment of water pollution.