Oil fouling is a key problem of superwettable oil–water separation membranes because the membranes are inevitably susceptible to varying degrees of oil contamination during the ongoing separation processes, which usually results in a severe impact on separation performance. Consequently, it is a great challenge to construct oil-removal membranes with superior resistance to oil contamination. Herein, we fabricated hierarchical double networks (HDT)-modified porous glass membrane with superhydrophilicity/underwater superoleophobicity. Firstly, a layer of silicone nanofilament (SNF) network bearing tremendous C = C double bonds were fabricated on a porous glass membrane surface by one-step chemical vapor deposition (CVD) using vinyltrichlorosilane (VTCS) as a precursor. Subsequently, the second network layer was constructed by copolymerization of the C = C double bonds on the SNF network and those in sulfobetaine-derived monomer (sulfobetaine methacrylate, SBMA), using N,N′-methylenebisacrylamide (MBA) as the cross-linkering agent. It was observed that the obtained HDT-modified glass membranes displayed excellent superhydrophilicity/underwater superoleophobicity accompanied with superior self-cleaning performance and oil-resistance properties. As a result, the HDT-modified membranes showed high separation flux and high efficiency for both oil/water mixtures (7500 L m−2h−1, above 99.98%) and surfactant-stabilized oil-in-water emulsions (1100 L m−2h−1, above 99.96%) with excellent cyclability. The outstanding advantages with characteristics of excellent oil resistance and superior separation performance enable the HDT-modified glass membrane promising applications in a wide range of industries related to oil–water separations.