Superhydrophobic surfaces have attracted extensive attentions due to their promising potential for broad applications. However, the complex preparation process and expensive low-surface-energy modifier significantly constrain its large-scale practical applications. Thus, construction of robust liquid-repellent surfaces via a facile and versatile approach without assistance of binder or post-modification is still highly desired and challenging. In this work, we synthesized superhydrophobic organic–inorganic coupling PVDF@SiO2 hybrid particles by thiol-ene click reaction using the branched thiol-terminated pentaerythritol tetra(3-mercaptopropionate) (PETMP) as cross-linking agent. The prepared PVDF@SiO2 hybrid particles could be used as building units to construct robust inorganic–organic composite superhydrophobic coating on various substrates through a simple spraying-curing process without any post-modification treatments. Owing to its high intermolecular cohesive force and self-film formation property of PVDF matrix, the fabricated coating possesses stable superhydrophobicity even after withstanding mechanical destruction or chemical harsh conditions. More importantly, the PVDF@SiO2 coating tremendously enhanced anti-corrosion property of Cu plate by orders of magnitude, with the corrosion current decreasing from 6.15 × 10–3 to 3.92 × 10–6 mA cm−2. Therefore, this strategy for constructing superhydrophobic composite coatings on various substrates could promote the advancement of interfacial superwetting technology and provide promising potentials for large-scale practical applications. [ABSTRACT FROM AUTHOR]