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Summary: The nontemplating preparation of porous carbon materials by using specially designed polymer precursors for supercapacitor is attracting considerable research attention because of the more controllable frame structure and easier processes than templating methods. Herein, a deliberately designed cross-linking polyphosphamide resin with defined N and P structure is synthesized and then carbonized to obtain porous carbon material. The as-obtained porous carbon material has a specific surface area of 2,620 m2 g−1, high porosity of 1.49 cm3 g−1, and well-distributed micro/mesoporous carbon structure. Different from activation by post-added NH4H2PO4, the confined N and P in the polymer frame are confirmed to play an important role in pore structure development by forming in situ highly dispersed NH4H2PO4 during carbonization. When evaluated as the electrode material for supercapacitors, the polyphosphamide-resin-based porous carbon material demonstrates excellent capacitance (440 F g−1 under 0.5 A g−1) and high stability (retention of 93% over 10,000 cycles). : Electrical Property; Polymers; Nanomaterials; Energy Materials Subject Areas: Electrical Property, Polymers, Nanomaterials, Energy Materials