Developing low-cost and high-performance metal-free oxygen reduction reaction (ORR) catalysts for fuel cells is highly desirable but still full of challenges. In this study, nitrogen and phosphorus co-functionalized three-dimensional (3D) porous carbon networks (NPCN) have been prepared by pyrolysis the zero-dimensional carbon quantum dots (CQDs) and a supermolecular gel of self-assembled melamine and amino trimethylene phosphonic acid (ATMP). The resultant NPCN catalysts possess unique 3D networks-like porous architecture, large specific surface area (743 m2 g−1) and abundant edge defects. As a catalyst for ORR, the optimized NPCN-900 (pyrolyzed at 900 °C) displays positive onset potential at 0.92 V and 0.74 V (vs. RHE) in alkaline and acidic media respectively, which are roughly close to those of Pt/C (0.93 V and 0.80 V). Additionally, the NPCN-900 exhibits longer-term stability and strong endurance to methanol over a wide pH range of aqueous media, which is much superior to that of Pt/C. Considering the outstanding activity of NPCN-900, it can be worked as a prospective metal-free catalyst to substitute commercial Pt/C for ORR in fuel cells. Display omitted