The construction of refined architectures plays a crucial role in performance improvement and application expansion of advanced materials. The synthesis of carbon microspheres with a refined hierarchical structure is still a problem in synthetic methodology, because it is difficult to achieve the necessary delicate control of the interior structure and outer shell across the microscale to nanoscale. Nitrogen‐doped multichamber carbon (MCC) microspheres with a refined hierarchical structure are realized here via a surfactant‐directed space‐confined polymerization strategy. The MCC precursor is not the traditional phenolic resol but a new kind of 2,6‐diaminopyridine‐based multichamber polymer (MCP) with a high nitrogen content up to 20 wt%. The morphology and sizes of MCP microspheres can be easily controlled by a dual‐surfactant system. The as‐synthesized MCC with a highly microporous shell, a multichamber inner core, and beneficial N‐doping can serve as a promising supercapacitor material.