The demand for efficient separation techniques in industries dealing with high viscosity emulsions has surged due to their widespread applications in various scenarios, including emulsion-based drug delivery systems, the removal of emulsified impurities in formulations and oil spill remediation. However, membrane fouling is a major challenge for conventional separation methods, leading to decreased efficiency and increased maintenance costs. Herein, a novel approach is reported by constructing liquid-like surfaces with double anti-fouling structure, incorporating soft nanomicelles within a rigid, chemically cross-linked network for both anti-membrane-fouling and effective viscous water-in-oil emulsion separation. The coating significantly outperforms perfluorinated and commercial polytetrafluoroethylene (PVDF) membranes, effectively preventing the adhesion of viscous oils like crude oil and pump oil, and alleviating severe membrane fouling. For high-viscosity emulsions (97.3 cP and 52.8 cP), it maintains over 99% separation efficiency after 3 h continuous use. Even after 15 h immersion in strong acids, alkalis, salts, or organic solvents, its separation efficiency remains above 95%. In addition, thanks to the anti-membrane-fouling ability, this work achieved 6 h continuous emulsion separation performance for the first time, demonstrating unparalleled long-term stability. Overall, this study offers valuable insights into the development of innovative coatings for efficient and eco-friendly separation of high-viscosity emulsions.