The cathode material properties of the microbial fuel cell (MFC) have a quite important effect on their power generation capacity. Excellent oxygen reduction reaction (ORR) performance is the key to obtaining the remarkable capability of MFC. In this study, a series of catalysts are successfully prepared by a simple step‐by‐step hydrothermal, in situ growth, solution polymerization, and pyrolysis procedure. Here, the NiCo nanoparticles loading on nitrogen/carbon dual‐doped matrix annealing at 800 °C (NiCo@DNC‐800) under Ar shows good ORR activity with a maximum power density of 2325.60 ± 41.96 mW m−2 in the case of the 2 mg cm−2 minimal catalyst loading, and which is about 2.16 times more than that achieved by 20% Pt/C (1074.21 ± 39.36 mW m−2). The unique N/C duel‐doped matrix provides more graphitic‐N and pyridinic‐N that can reduce the resistance of electron diffusion and transport, together with the synergistic catalysis of NiCo active sites improving the oxygen reduction reaction performance of MFC greatly. In addition, the NiCo@DNC‐800 cathode catalyst demonstrates that composite materials have great application potential in water pollution treatment and new green energy strategies.
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