Hitherto, various sulfite-based advanced oxidation processes have emerged with particular vantages of low cost and potential for efficient contaminant degradation, which still requires increasing strategies for addressing its drawback. To achieve system-neutral feasibility and overcome the limitations, a metal oxide composite catalyst Hematite/Fe2TiO5 integrated with S-scheme heterojunction was constructed for ofloxacin degradation under S (IV)-visible light conditions. Impressively, the as-built system manifested significant promotion on substrate removal (more than four times the original Fe2TiO5), which indicated the accelerated inner-sphere interactions between catalyst and S(IV) with beneficial Vis contributed primarily to the degradation, demonstrating the dual sulfite-mediated effective pathway through modulated photogenerated carriers and oxy-sulfur radical chain reactions. Additionally, the interfacial enhancement by the heterojunction structure was further investigated by First-principles computation, which confirmed the mechanism of facilitated electron-hole pair separation. Overall, this work reveals the critical mechanism of Vis-induced S(IV)-AOP and provides constructive perspectives to address the limitations of conventional processes.