<p>Phenolic compounds in phenolic wastewater greatly harm the human body and aquatic ecosystem, even at low concentrations. Therefore, it is of great significance to effectively remove phenolic wastewater. A polyvinylidene fluoride (PVDF)/polydimethylsiloxane (PDMS) composite fiber membrane was used to treat phenol wastewater. Due to the limited hydrophilicity and hydrophobicity of the membrane, the membrane's separation ability was limited. In this paper, superhydrophobic fluorinated silica (F-SiO₂) nanoparticles were prepared, and F-SiO₂-PVDF/PDMS inorganic–organic blend membranes were prepared by electrospinning. The effects of F-SiO₂ mass ratio on the microstructure and hydrophobic properties of PVDF/PDMS organic membranes were investigated and characterized by scanning electron microscopy (SEM), thermogravimetric (TG), contact angle (JC2000DF), and other test methods. The results show that when the mass ratio of F-SiO₂ is 1.5%, the composite membrane has the best film-forming property, good mechanical properties, and thermal stability. The hydrophobic angle reaches 153.9°, and the phenol removal rate reaches 46.8% after 24&#xa0;h. The membrane realizes the ideal superhydrophobic surface state, and the organic hydrophobic performance is greatly improved, which can effectively treat phenol wastewater.</p> Graphical abstract <p></p>