The　removal　of　ethane　(C2H6)　from　its　analogous　ethylene　(C2H4)　is　of　paramount　importance　in　the　petrochemical　industry,　but　highly　challenging　due　to　their　similar　physicochemical　properties.　The　use　of　emerging　porous　organic　cage　(POC)　materials　for　C2H6/C2H4　separation　is　still　in　its　infancy.　Here,　we　report　the　benchmark　example　of　a　truncated　octahedral　calix[4]resorcinarene-based　POC　adsorbent　(CPOC-301),　preferring　to　adsorb　C2H6　than　C2H4,　and　thus　can　be　used　as　a　robust　absorbent　to　directly　separate　high-purity　C2H4　from　the　C2H6/C2H4　mixture.　Molecular　modelling　studies　suggest　the　exceptional　C2H6　selectivity　is　due　to　the　suitable　resorcin[4]arene　cavities　in　CPOC-301,　which　form　more　multiple　C-H　hydrogen　bonds　with　C2H6　than　with　C2H4　guests.　This　work　provides　a　fresh　avenue　to　utilize　POC　materials　for　highly　selective　separation　of　industrially　important　hydrocarbons.　The　removal　of　ethane　from　ethylene　is　of　importance　in　the　petrochemical　industry,　but　similar　physicochemical　properties　of　these　molecules　makes　separation　a　challenging　task.　Here,　the　authors　demonstrate　that　a　robust　octahedral　calix[4]resorcinarene-based　porous　organic　cage　can　separate　high-purity　ethylene　from　ethane/ethylene　mixtures.