A new nitrogen-rich microporous polymer (PAN-FPP5) containing pillar[5]arene macrocycles was fabricated via facile polycondensation between pillar[5]arene-based monomer (FPP5) bearing two aldehyde moieties and melamine. Compared with the macrocycle-free category, PAN-FPP5 exhibited superior CO2 uptake (12.5 wt % vs 9.9 wt %, 273 K/1 bar) and selectivity of CO2/N-2 (55.6 vs 39.9, 298 K). In addition, PAN-FPP5 also displayed an excellent capability of removal of iodine in both solvent and vapor phases because of the electron-rich property of pillar[5]arene.