Carbon dioxide capture from point sources like coal-fired power plants is considered to be a solution for stabilizing the CO(2) level in the atmosphere to avoid global warming. Methane is an important energy source that is often highly diluted by nitrogen in natural gas. For the separation of CO(2) and CH(4) from N(2) in flue gas and natural gas, respectively, sorbents with high and reversible gas uptake, high gas selectivity, good chemical and thermal stability, and low cost are desired. Here we report the synthesis and CO(2), CH(4), and N(2) adsorption properties of hierarchically porous electron-rich covalent organonitridic frameworks (PECONFs). These were prepared by simple condensation reactions between inexpensive, commercially available nitridic and electron-rich aromatic building units. The PECONF materials exhibit high and reversible CO(2) and CH(4) uptake and exceptional selectivities of these gases over N(2). The materials do not oxidize in air up to temperature of 400 °C.