Superhydrophilic membrane materials are widely used for oil/water separation due to their excellent resistance to anti-fouling underwater. The key factors for realizing superhydrophilicity of membranes are the introduction of hydrophilic groups and the construction of surface micro/nano roughness structures. Herein, we propose a simple, mild, and green dip-coating method to prepare silk fibroin (SF)-tannic acid (TA)@CaCO3 hybrid film to achieve superhydrophilicity of polypropylene nonwovens (PP). Specifically, the hydrophobic interactions between SF and hydrophobic materials were used to create the pre-coatings. TA molecules were deposited onto the surface of SF via hydrogen bonding to provide phenolic hydroxyl groups for achieving the hydrophilicity of PP membranes. Then, the CaCO3 was synthesized in situ by introducing Ca2+ into the pre-coating while depositing TA to construct micro/nano-roughness structures on the PP membrane surface for obtaining superhydrophilicity. PP-SF-TA@CaCO3 membranes exhibit outstanding superhydrophilicity and underwater superoleophobicity, with separation efficiencies exceeding 99 % for a variety of oil–water mixtures and oil-in-water emulsions, and water fluxes ranging from 4000 L m-2h−1 to 5500 L m-2h−1. The separation efficiencies remained above 99 % throughout 50 separation cycles, indicating the excellent separation stability of the modified membranes. Moreover, no significant loss of separation efficiency was observed when separating oil mixtures from harsh water sources, including acidic, alkaline, cold, and hot water. Therefore, the membranes modified by the above process have a promising application in the practical separation of oily wastewater.