| Summary: | Chitosan, a biomass raw material, was utilized as a carbon skeleton source and served as a nitrogen (N) atom dopant in this study. By co-doping phosphorus (P) atoms from H<sub>3</sub>PO<sub>4</sub> and nitrogen (N) atoms with a carbon (C) skeleton and hybridizing them with Mn<sub>3</sub>O<sub>4</sub> on a carbon fiber cloth (CC), an Mn<sub>3</sub>O<sub>4</sub>@NPC/CC electrode was fabricated, which exhibited an excellent capacitive performance. The N, P-codoped carbon polycrystalline material was hybridized with Mn<sub>3</sub>O<sub>4</sub> during the chitosan carbonization process. This carbon polycrystalline structure exhibited an enhanced conductivity and increased mesopore content, thereby optimizing the micropore/mesopore ratio in the electrode material. This optimization contributed to the improved storage, transmission, and diffusion of electrolyte ions within the Mn<sub>3</sub>O<sub>4</sub>@NPC electrode. The electrochemical behavior was evaluated via cyclic voltammetry and galvanostatic charge–discharge tests using a 1 M Na<sub>2</sub>SO<sub>4</sub> electrolyte. The capacitance significantly increased to 256.8 F g<sup>−1</sup> at 1 A g<sup>−1</sup>, and the capacitance retention rate reached 97.3% after 5000 charge/discharge cycles, owing to the higher concentration of the P-dopant in the Mn<sub>3</sub>O<sub>4</sub>@NPC/CC electrode. These findings highlight the tremendous potential of flexible supercapacitor electrodes in various applications.
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