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Oxygen reduction reaction (ORR) is the major reaction that occurs at the cathodes of fuel cells and metal–air batteries. Development of inexpensive, active, and durable heteroatom doped carbon-based ORR catalysts can lead to significant cost reduction of these electrochemical energy devices, which therefore has recently attracted enormous research attentions. This work reports a three-dimensional porous composite (P-g-C₃N₄@NH₂–CB) for the highly efficient ORR catalyst. P-g-C₃N₄@NH₂–CB was prepared by mixing phosphorus-doped graphitic carbon nitride nanosheets (P-g-C₃N₄ NSs) with NH₂-functionalized carbon black (NH₂–CB) via a novel self-assembly approach. The NH₂–CB was rationally chosen as the spacer that enables the self-assembled with the P-g-C₃N₄ NSs driven by the electrostatic interaction. The intercalation of NH₂–CB induces the transformation of 2-D P-g-C₃N₄ NSs into a 3-D …