Physisorption-based　separation　processes　represents　a　promising　alternative　to　the　conventional　thermally　driven　methods,　such　as　cryogenic　separation.　However,　a　significant　challenge　lies　in　balancing　the　trade-off　between　adsorption　capacity　and　selectivity　of　adsorbents.　In　this　study,　we　introduce　a　novel　fluorinated-anion　pillared　metal-organic　frameworks　(APMOFs)　featuring　a　dual-pore　architecture,　constructed　using　a　pyridine-oxazole　bifunctional　ligand.　The　inherent　low　symmetry　of　the　ligand　leads　to　significant　distortion　of　the　fluorinated-anion　pillars,　resulting　in　a　distinctive　type　of　APMOFs　characterized　by　dual-pore　architecture.　On　pore　structure　with　constrict　pore　width　is　enriched　with　a　high　density　of　anion　fluorinated　pillars,　offering　numerous　active　sites　advantageous　for　enhancing　separation　selectivity.　Concurrently,　the　other　pore　structure　exhibits　larger　dimensions,　facilitating　increased　gas　molecule　accommodation　and　thereby　augmenting　adsorption　capacity.　Gas　sorption　studies　reveal　a　substantial　C2H2　adsorption　capacity　and　a　high　C2H2/CO2　separation　selectivity.　Breakthrough　experiments　confirm　its　exceptional　separation　performance,　while　theoretical　investigations　elucidate　a　sequential　adsorption　process　within　these　APMOFs,　underscoring　the　efficacy　of　this　strategy　in　overcoming　trade-off　limits　in　adsorbents.　©　2024　Wiley-VCH　GmbH.