Benefiting　from　highly　tunable　pore　environments,　some　metal-organic　frameworks　(MOFs)　have　recently　shown　promising　prospects　in　the　separation　of　methanol-to-olefin　(MTO)　products　(mainly　C3H6　and　C2H4).　However,　the　“trade-off”　between　gas　storage　capacity　and　selectivity　always　results　in　inefficient　separation.　In　addition,　poor　stability　of　MOFs　also　limits　practical　separation　applications.　Herein,　we　have　successfully　assembled　a　layered　Y-MOF　(FJI-W9)　with　bent　diisophthalate　ligands　(H4L),　Y-O　chains,　and　2-fluorobenzoic　acids.　As　expected,　FJI-W9　not　only　exhibits　good　chemical　stability　but　also　shows　significant　potential　for　C3H6/C2H4　separation.　For　FJI-W9,　the　C3H6　uptake　at　298　K　and　10　kPa　is　63　cm3/g,　and　the　IAST　selectivity　of　FJI-W9　for　C3H6/C2H4　(V/V　=　50/50)　is　calculated　to　be　20.5.　To　the　best　of　our　knowledge,　both　C3H6　uptake　and　selectivity　of　FJI-W9　surpass　most　porous　materials.　GCMC　simulation　indicates　that　the　special　supramolecular　binding　sites　in　FJI-W9　have　much　stronger　interactions　with　C3H6　than　C2H4　molecules.　More　importantly,　practical　breakthrough　experiments　demonstrate　that　FJI-W9　can　effectively　separate　C3H6/C2H4　(50/50)　mixtures,　thus　obtaining　high-purity　C2H4　and　C3H6,　respectively.　©　2024　American　Chemical　Society.