Superwettability materials have focused considerable interest of researchers due to their extensive applications like oil/water separation. Currently, the development of materials with controllable wettability for efficient on-demand oil/water separation is highly desired. In this work, we constructed caterpillar-like cobalt-nickel hydroxide/carbon cloth hierarchical architecture via in situ hydrothermal growth. Interestingly, this hierarchical architecture shows reversible wettability after immersing in stearic acid ethanol solution and tetrahydrofuran, which can be used for efficient on-demand oil/water separation. This hierarchical architecture is proved to have excellent environmental and mechanical durability. Moreover, the fluid-based gating and liquid-infusion-interface mechanism are presented to explain oil/water separation process. The caterpillar-like cobalt-nickel hydroxide/carbon cloth with low cost and simple preparation shows a promising prospect in the application of efficient on-demand oil/water separation.