A new porous organic polymer PDVBTT-1 (poly-divinylbenzene-co-triallyloxytriazine) has been synthesized through radical co-polymerization utilizing two monomers, that is, divinylbenzene and 2,4,6-triallyloxy-1,3,5-triazine in the presence of AIBN (azobisisobutyronitrile) as a radical initiator under solvothermal conditions in the absence of any structure directing agent. The polymer has been characterized thoroughly by N-2 sorption, FTIR, UV/Vis, and solid-state C-13 cross-polarization magic angle spinning (CP MAS) NMR spectroscopy, field emission FE-SEM, high-resolution HR-TEM, and thermogravimetric/differential thermal analysis (TG/DTA). Owing to the considerably good surface area of 644 m(2)g(-1) and surface basic sites (1.10 mmolg(-1)), the material showed very good CO2 adsorption properties. Furthermore, the porous polymer showed good catalytic activity in the base-catalyzed, one-pot, multicomponent condensation reaction between various substituted aromatic aldehydes, malononitrile, and activated phenols such as 2-naphthol, resorcinol, etc., for the synthesis of 2-amino-chromenes in water and under solvent-free microwave irradiation conditions. This N-rich porous polymer is highly recyclable and thus it has potential for a wide range of base-catalyzed organic transformations in the future.