Low-cost and scalable superhydrophobic coating methods provide viable approaches for energy-efficient separation of immiscible liquid/liquid mixtures. A scalable photopolymerization method is developed to functionalize porous substrates with a hybrid coating of tetrapodal ZnO (T-ZnO) and polymethacrylate, which exhibits simultaneous superhydrophobicity and superoleophilicity. Here, T-ZnO serves dual purposes by (i) initiating radical photopolymerization during the fabrication process through a hole-mediated pathway and (ii) providing a hierarchical surface roughness to amplify wettability characteristics and suspend liquid droplets in the metastable Cassie-Baxter regime. Photopolymerization provides a means to finely control the conversion and spatial distribution of the formed polymer, whilst allowing for facile large-area fabrication and potential coating on heat-sensitive substrates. Coated stainless-steel meshes and filter papers with desired superhydrophobic/superoleophilic properties exhibit excellent performance in separating stratified oil/water, oil/ionic-liquid, and water/ionic-liquid mixtures as well as water-in-oil emulsions. The hybrid coating demonstrates desired mechanical robustness and chemical resistance for their long-term application in large-scale energy-efficient separation of immiscible liquid/liquid mixtures.