Abstract We have adopted the concept of “cage to frameworks” to successfully produce a Na–N connected coordination networked cage Na‐NC1 by using a [3+6] porous imine‐linked organic cage NC1 (Nanjing Cage 1) as the precursor. It is found that Na‐NC1 exhibits hierarchical porosity (inherent permanent voids and interconnected channel) and gas sorption measurements reveal a significantly enhanced CO 2 uptake (1093 cm 3 g −1 at 23 bar and 273 K) than that of NC1 (162 cm 3 g −1 under the same conditions). In addition, Na‐NC1 exhibits very low CO 2 adsorption enthalpy making it a good candidate for porous materials with both high CO 2 storage and low adsorption enthalpy.