<p>The precise control of the chemical composition and surface structure of the porous carbon material is crucial for high-efficiency energy storage. Herein, a local oxygen exchange strategy between KSCN and the carbon skeleton is proposed to precisely modulate the pore structure, nitrogen species, and carbon layer thickness of the resin-derived hollow carbon spheres. It is found that the additional sulfur doping modulates the valence bands of edge-nitrogen sites, creatively realizing the conversion of nitrogen oxides into edge-nitrogen species within the carbon matrix. Moreover, the product K₂SO₄ acts as a mesoporous template and activator, not only forming about 3.1 nm mesoporous within carbon shell but also regulating the thickness and the graphitization degree. Consequently, the optimized NSMHCS-0.6 demonstrates superior electrochemical performance, delivering a high capacitance of 304.3 F g⁻¹ in supercapacitors and a specific capacity of 264.1 mAh g⁻¹ in zinc-ion hybrid capacitors, along with exceptional cycling stability (90.9% retention after 20000 cycles at 5 A g⁻¹). Density functional theory (DFT) calculations, <i>ex-situ</i> XPS and kinetic analyses further revealed that the enhanced storage capacity is due to the synergistic effect of abundant edge-nitrogen active sites and hierarchical porous structure. This work provides an effective approach for designing high-performance carbon nanomaterials for advanced energy storage applications.</p>