Water‐in‐oil emulsions separation plays a critical role in industrial wastewater treatment. Membrane technology has attracted much interest in water‐in‐oil emulsions separation field for its excellent separation performance and facile processing method. However, versatile membrane with better solvent‐resistance is still absent in chemical industry. In this work, oxidized polyarylene sulfide sulfone (O‐PASS) membrane was severed as substrate, on which a hydrophobicity surface was built via coating of octadecyltrichlorosilane (OTS). And polydopamine (PDA) layer was employed and acted as connector between OTS and O‐PASS membrane due to its abundant active hydroxyl group. The maximum water contact angle was 132.6° indicating good hydrophobicity of the membrane. Finally, the OTS/PDA/O‐PASS composite membranes showed good separation performance for corrosive emulsions: the rejection and flux were 93.0% and 10.0 L/m2h for water‐in‐dichloromethane emulsions, and the rejection and flux were 92.3% and 34.6 L/m2h for water‐in‐n‐hexane emulsions. The OTS/PDA/O‐PASS composite membrane is a new candidate membrane for water‐in‐oil emulsions separation. In addition, the superior performance of the composite membrane under harsh environment conditions ensures its usefulness in resistance aggressive solvent.