Ordered mesoporous carbon materials offer robust network of organized pores for energy storage and catalysis applications, but suffer from time‐consuming and intricate preparations hindering their widespread use. Here we report a new and rapid synthetic route for a N‐doped ordered mesoporous carbon structure through a preferential heating of iron oxide nanoparticles by microwaves. A nanoporous covalent organic polymer is first formed in situ covering the hard templates of assembled nanoparticles, paving the way for a long‐range order in a carbonaceous nanocomposite precursor. Upon removal of the template, a well‐defined cubic mesoporous carbon structure was revealed. The ordered mesoporous carbon was used in solid state hydrogen storage as a host scaffold for NaAlH4, where remarkable improvement in hydrogen desorption kinetics was observed. The state‐of‐the‐art lowest activation energy of dehydrogenation as a single step was attributed to their ordered pore structure and N‐doping effect.

NaAlH4 nanoconfined in a graphene oxide framework (NaAlH4@GOF) showed significantly enhanced hydrogen storage kinetics as well as improved oxidative stability under ambient conditions.