Polymer-dominated membranes with switchable wettability are highly desired due to their on-demand applications for oil/water separation. Herein, a low-cost methodology to fabricate membranes consisting of hyperbranched polyurethane (HBPU) and fluorine-modified silica (F-SiO2) with tunable wettability by electrospinning is reported. The HBPU/F-SiO2 composite membranes can be transformed from superhydrophobicity to -philicity through plasma treatment; these membranes exhibit different wettability for effective separation of surfactant-stabilized water-in-oil and oil-in-water emulsions.