In this work, the superhydrophobic fabric was fabricated by surface modification with mercaptopropyltriethoxysilane to incorporate thiol groups and subsequent thiol-ene click chemistry with methacryloxypropyltrimethoxysilane (MPS)-modified SiO2@Fe3O4 nanoparticles (MPS-SiO2@Fe3O4) in the assistance of ultraviolet light. The Fourier-transform infrared, X-ray photoelectron spectroscopy, and scanning electron microscopy measurement results demonstrated that the MPS-SiO2@Fe3O4 nanoparticles were strongly grafted onto the fabric surface via a chemically covalent bond and constructed a hierarchical micro/nanoscale structure combined with the inherent microstructure of pristine fabric. Under combination of such hierarchical structures and the inherent low surface energies of hydrophobic Si skeleton and alkyl groups, the resulting fabric exhibited superhydrophobicity and could be used to separate oil from the oil/water mixture accompanying with high separation efficiency, permeate flux, and excellent recyclability. Furthermore, the as-prepared fabric displayed excellent superhydrophobic durability against tape-peeling, abrasion, and chemicals like strong acidic and alkaline solutions, which should be ascribed to the strong interactions between the MPS-SiO2@Fe3O4 and fabric surface by strong chemical bonds. Therefore, this work not only provided a facile, environmentally friendly, and versatile strategy for fabricating the superhydrophobic composites but also opened a door to preserve the durable superhydrophobicity, exhibiting promising prospect in the application of oil/water separation.