Searching　for　porous　materials　that　can　safely　store　and　efficiently　separate　acetylene　(C2H2),　a　commonly　used　petrochemical　feedstock　with　highly　explosive　properties,　is　a　pressing　and　significant　task.　Nitrogen-rich　porous　materials　have　garnered　substantial　attention　for　their　ability　to　interact　strongly　with　acidic　C2H2.　Herein,　we　report　two　novel　nitrogen-rich　porous　organic　cages　(POCs),　namely　CPOC-107　and　CPOC-203,　constructed　from　the　same　bowl-shaped　tetraformylcalix[4]resorcinarene　but　different　nitrogen-rich　imidazolium-based　diamine　synthons.　X-ray　crystallographic　analysis　reveals　that　CPOC-107　adopts　a　[2　+　4]　lantern-shaped　structure,　whereas　CPOC-203　takes　on　a　[3　+　6]　triangular　prism　shape.　Moreover,　the　cages　exhibit　large　cavity　volumes　of　up　to　787　Å3　and　high　specific　surface　areas　of　up　to　1202　m2　g−1.　Owing　to　their　high　surface　areas　and　high　nitrogen　content,　both　cages　exhibit　impressive　C2H2　adsorption　capabilities.　Specifically,　CPOC-107　achieves　a　remarkable　C2H2　uptake　value　of　up　to　146　cm3　g−1　at　298　K　and　1　atm,　the　highest　among　those　reported　for　all　porous　organic　materials　to　date.　Moreover,　experimental　breakthrough　tests　have　confirmed　the　effective　separation　of　C2H2/CO2　mixtures　using　the　CPOC-107　adsorbent.　©　2023　The　Royal　Society　of　Chemistry.