The challenges posed by the non-conductive nature of iodine, coupled with the easy formation of soluble polyiodides in water, impede its integration with zinc for the development of advanced rechargeable batteries. Here we demonstrate the in-situ loading of molybdenum carbide nanoclusters (MoC) and zinc single atoms (Zn-SA) into porous carbon fibers to invoke electrocatalytic conversion of iodine at the interface. The electronic interactions between MoC and Zn-SA lead to an upshift in the d-band center of Mo relative to the Fermi level, thus promoting the interfacial interactions with iodine species to suppress shuttle effects. Notably, the optimal charge delocalization, induced by d-p orbital hybridization between molybdenum and iodine, also lowers the redox energy barrier to promote the interfacial conversion. With interfacial electrocatalysis minimizing polyiodide intermediates via a favorable redox conversion pathway, zinc-iodine batteries therefore demonstrate a large specific capacity of 230.6 mAh g