Abstract: The shuttle effect induced by the dissolution of polyiodides constitutes a critical challenge constraining the performance of zinc-iodine batteries (Zn−I₂). As one of the vital electrode materials for Zn−I₂ batteries, the pore structure and surface chemical composition of porous carbon materials significantly influence the performance of Zn−I₂ batteries. In this study, a hundred-gram-scale ZIF-8@ZnO composite was synthesized via mechanical ball- milling using nano-ZnO as both a structural template and metal ion source. Serving as carbon precursors, these composites were subjected to high-temperature pyrolysis, leveraging the physical confinement effect of nano-ZnO and the inherent microporosity/nitrogen-rich characteristics of ZIF-8, to obtain nitrogen-doped porous carbons (denoted as NC-x, where x represents the pyrolysis temperature) featuring co-existing mesopores and micropores. The NC-x materials were applied as cathodes in aqueous Zn−I₂ batteries, and systematic investigations were conducted to elucidate the influence of pore architecture and nitrogen doping configurations on battery performance. Specifically, mesopores shortened the diffusion pathways of the KI electrolyte and effectively confined polyiodide intermediates, while micropores facilitated strong adsorption of I⁻ ions and suppressed I₃⁻ formation. Graphitic nitrogen within the carbon framework significantly enhanced electrical conductivity, whereas pyridinic and pyrrolic nitrogen species acted as chemisorption sites to strengthen interactions between iodine species and the carbon matrix, thereby effectively mitigating the shuttle effect. Benefiting from optimal pore structure, N-doping types and percentage of atomic quantity, NC-1000 exhibits superior electrochemical performance: high capacity (248.6 mAh/g at 1 A/g), outstanding rate capability (86.1 mAh/g retained at 20 A/g), and exceptional cycling stability (90% capacity retention after 16 000 cycles at 10 A/g). In conclusion, rational pore design and surface composition regulation significantly enhance the performance of porous carbon-based Zn−I₂ batteries.