Here, we report a porous covalent triazine-piperazine linked polymer (CTPP) featuring 3D nano flower morphology and enhanced capture/removal of CO2, CH4 from air (N-2), essential to control greenhouse gas emission and natural gas upgrading. C-13 solid-state NMR and FTIR analyses and CHN and X-ray photoelectron spectroscopy (XPS) elemental analyses confirmed the integration of triazine and piperazine components in the network. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) analyses revealed a relatively uniform particle size of approximately 400-500 nm with 3D nanoflower microstructure, which was formed by the self assembly of interwoven and slight bent nanoflake components. The material exhibited outstanding chemical robustness under acidic and basic medium and high thermal stability up to 773 K. The CTPP possess high surface area (779 m(2)/g) and single-component gas adsorption study exhibited enhanced CO2 and CH4 uptake of 3.48 mmol/g, 1.09 mmol/g, respectively at 273 K, 1 bar; coupled with high sorption selectivities for CO2/N-2 and CH4/N-2 of 128 and 17, respectively. The enriched Lewis basicity of the CTPP favors the interaction with CO2, which results in an enhanced CO2 adsorption capacity and high CO2/N-2 selectivity. The binary mixture breakthrough study for the flue gas composition at 298 K showed a high CO2/N-2 selectivity of 82. CO2 heats of adsorption for the CTPP (34 kJ mol(-1)) were realized at the borderline between strong physisorption and weak chemisorption (Q(stCO2); 25-50 kJ mol(-1)) and low Q(st) value for N-2 (22.09 kJ mol(-1)), providing the ultimate validation for the high selectivity of CO2 over N-2. (C) 2016 Elsevier Ltd. All rights reserved.