Pore wetting is undesirable in the membrane gas�liquid separation process as it deteriorates the gas removal flux. To alleviate the affinity of a membrane surface toward a liquid solvent, its hydrophobicity needs to be enhanced. In this study, a superhydrophobic polyvinylidene fluoride-co-hexafluoropropylene membrane was synthesized via a simple and facile nonsolvent-induced phase inversion process. Hydrophobic nano-SiO2 particles were used as solvent additives to improve the wetting resistance of the membrane. The results revealed that blended nano-SiO2 membranes exhibited enhanced surface hydrophobicity in terms of water contact angle. Such improvement was attributed to the enhancement of surface roughness via the formation of hierarchical multilevel protrusions. Besides, the embedment of nanoparticles in polymer spherulitic globules also contributed to the reduction in surface energy of the membrane. As a result, the blended nano-SiO2 membrane achieved superhydrophobicity with a water contact angle of up to 151°. © 2019 Académie des sciences