Cyclophosphazene-based inorganic organic hybrid nanoporous materials (CHNMs) have been synthesized by a facile solvothermal method. The condensation of pyrrole with the reaction product of phosphonitrilic chloride trimer and 4-hydroxybenzaldehyde resulted in the formation of high surface-area CHNMs. The maximum specific surface area (SABET) of 1328 m(2) g(-1) with hierarchical pore structures having micropores centered at 1.18 nm and mesopores in the range of 2.6-3.6 nm was estimated from the N-2 sorption analysis. Observation of high SABET could be attributed to the synergy effect exerted by the cyclophosphazene moiety owing to its three-dimensional paddle wheel structure. The metal-free adsorbent exhibited a high and reversible CO, uptake of 22.8 wt % at 273 K and 1 bar. The performance is on the higher side among the reported metal-free inorganic-organic hybrid nanoporous adsorbents. Moreover, the high H-2 uptake of 2.02 wt % at 77 K and 1 bar is an added advantage. The superior performance of the adsorbents for the gas sorption applications could be attributed to the combined effect of high SA(BET) and hierarchical pore structure, which has made CHNMs good candidates for energy and environmental applications.