Due　to　the　trade-off　between　purity　and　flux,　the　development　of　high-purity,　high-flux　oil–water　separation　materials　is　still　an　arduous　challenge.　Herein,　to　achieve　emulsion　separation　with　high　purity　and　high　permeability,　fluorinated　graphene/poly(vinyl　alcohol)　aerogel　(FGPA)　with　strong　honeycomb　was　obtained　via　a　facile　freeze-drying　method,　and　the　separation　mechanism　was　investigated　via　computational　fluid　dynamics　(CFDs)　simulation.　The　as-prepared　FGPA　exhibited　superhydrophobicity-superoleophobicity　and　cyclic　compression　stability.　Under　the　complex　pore　and　superhydrophobicity,　FGPA　could　separate　water-in-oil　emulsions　with　droplet　sizes　several　times　smaller　than　their　own　aperture　only　under　gravity　with　ultrahigh　flux　(3255　L　m−2 h−1)　and　ultrahigh　purity　(99.9%).　Also,　the　separation　process　as　visualized　using　simulations　revealed　that　the　vortex　accelerates　the　demulsification　behavior　and　promotes　the　gathering　of　water　droplets　rebounding　on　the　superhydrophobic　surface,　so　that　the　water　droplets　are　intercepted.　Therefore,　FGPA　has　broad　practical　application　potential　in　high-flux　and　high-purity　oil–water　emulsion　separation.　©　2022　American　Institute　of　Chemical　Engineers.