AbstractSmart membranes with responsive wettability show promise for controllably separating oil/water mixtures, including immiscible oil-water mixtures and surfactant-stabilized oil/water emulsions. However, the membranes are challenged by unsatisfactory external stimuli, inadequate wettability responsiveness, difficulty in scalability and poor self-cleaning performance. Here, we develop a capillary force-driven confinement self-assembling strategy to construct a scalable and stable CO₂-responsive membrane for the smart separation of various oil/water systems. In this process, the CO₂-responsive copolymer can homogeneously adhere to the membrane surface by manipulating the capillary force, generating a membrane with a large area up to 3600 cm² and excellent switching wettability between high hydrophobicity/underwater superoleophilicity and superhydrophilicity/underwater superoleophobicity under CO₂/N₂ stimulation. The membrane can be applied to various oil/water systems, including immiscible mixtures, surfactant-stabilized emulsions, multiphase emulsions and pollutant-containing emulsions, demonstrating high separation efficiency (>99.9%), recyclability, and self-cleaning performance. Due to robust separation properties coupled with the excellent scalability, the membrane shows great implications for smart liquid separation.