Since superwetting surfaces have emerged, on-demand oil/water separation materials serve as a new direction for meeting practical needs. This new separation mode uses a single porous material to allow oil-removing and water-removing to be achieved alternately. In this review, the fundamentals of wettability are systematically summarized in oil/water separation. Most importantly, the two states, bioinspired surface and intelligent surface, are summarized for on-demand oil/water separation. Specifically, bioinspired surfaces include micro/nanostructures, bioinspired chemistry, Janus-featured surfaces, and dual-superlyophobic surfaces that these superwetting materials can possess asymmetric wettability in one structure system or opposite underliquid wettability by prewetting. Furthermore, an intelligent surface can be adopted by various triggers such as pH, thermal and photo stimuli, etc., to control wettability for switchable oil/water separation reversibly, expressing a thought beyond nature to realize innovative oil/water separation by external stimuli. Remarkably, this review also discusses the advantages of all the materials mentioned above, expanding the separation scope from the on-demand oil/water mixtures to the multiphase immiscible liquid-liquid mixtures. Finally, the prospects of on-demand oil/water separation materials are also concluded.