The feasible capture and separation of CO2 and N-2 from CH4 is an important task for natural gas upgrading and the control of greenhouse gas emissions. Here, we studied the microporous covalent imine networks (CIN) material prepared through Schiff base condensation and exhibited superior chemical robustness under both acidic and basic conditions and high thermal stability. The material possesses a relatively uniform nanoparticle size of approximately 70-100 nm. This network featured permanent porosity with a high surface area (722 m(2)/g) and micropores. A single-component gas adsorption study showed enhanced CO2 and CH4 uptakes of 3.32 mmol/g and 1.14 mmol/g, respectively, at 273 K and 1 bar, coupled with high separation selectivities for CO2/CH4, CH4/N-2, and CO2/N-2 of 23, 11.8 and 211, respectively. The enriched Lewis basicity in the porous skeletons favours the interaction of quadrupolar CO2 and polarizable CH4, resulting in enhanced CH4 and CO2 uptake and high CH4/N-2, CO2/CH4 and CO2/N-2 selectivities. Breakthrough experiments showed high CO2/CH4, CH4/N-2 and CO2/N-2 selectivities of 7.29, 40 and 125, respectively, at 298 K and 1 bar. High heats of adsorption for CH4 and CO2 (Qst(CH4); 32.61 kJ mol(-1) and Qst(CO2); 42.42 kJ mol(-1)) provide the ultimate validation for the high selectivity. To the best of our knowledge, such a versatile adsorbent material that displays both enhanced uptake and selectivity for a variety of binary gas mixtures, including CO2/CH4, CO2/N-2 and CH4/N-2, has not been extensively explored. (C) 2016 Elsevier B.V. All rights reserved.