The　exploration　of　ethane　(C2H6)-selective　porous　materials　for　the　direct　production　of　polymer-grade　ethylene　(C2H4)　from　a　C2H6/C2H4mixture　in　a　single　energy-saving　adsorption　step　is　of　utmost　importance　but　remains　a　significant　challenge.　Thus,　developing　robust　C2H6-selective　adsorbents　with　high　C2H6capacity　and　C2H6/C2H4selectivity　is　urgently　needed　for　industrial　applications.　In　this　study,　we　have　successfully　designed　and　synthesized　two　novel　calix[4]resorcinarene-based　porous　organic　cages　(POCs)　named　CPOC-501　and　CPOC-502.　The　POCs　were　formed　via　a　Schiff-base　reaction　involving　face-directed　[6+8]　condensation　between　a　bowlshaped　tetratopic　tetraformylcalix[4]resorcinarene　and　triangular　tritopic　amine　synthons.　Analysis　using　single　crystal　X-ray　crystallography　revealed　that　both　cages　possess　large　truncated　octahedral　cavities　with　a　volume　of　approximately　6500　Å3　and　12　accessible　rhombic　windows　with　a　side　length　of　approximately　10.5　Å.　Furthermore,　the　cages　exhibited　excellent　chemical　stability　under　neutral,　acidic,　and　basic　conditions　and　high　Brunauer-Emmett-　Teller　specific　surface　areas　of　up　to　2175　m2　g-1　after　desolvation.　Both　POCs　demonstrated　superior　adsorption　capabilities　for　C2H6over　C2H4.　Notably,　CPOC-502　exhibited　a　C2H6capacity　and　C2H6/C2H4selectivity　of　83　cm3　g-1　and　2.83,　respectively,　surpassing　most　of　the　best-performing　C2H6-selective　porous　organic　materials　reported　to　date.　Moreover,　breakthrough　experiments　confirmed　that　both　cages　efficiently　produced　polymer-grade　C2H4(＞99.9%)　directly　from　the　C2H6/C2H4mixture,　highlighting　their　outstanding　recyclability.　©　2024　Chinese　Chemical　Society.　All　rights　reserved.