To address the issues of ZVI's susceptibility to oxidation and aggregation, ball milling and Na 2 S·9H 2 O modification were employed on ZVI to enhance its efficiency in removing Cr(VI) from effluent. The characterization results expressed that S-mZVI bm had mesoporous and macroporous structures, enabling successful capture of Cr(VI). Moreover, S-mZVI bm had the highest adsorption capacity for Cr(VI) (350.04 mg/g) at pH = 2.00 and reached kinetic equilibrium within 420 min. Furthermore, the adsorption of Cr(VI) by S-mZVI bm conformed to the Avrami-fractional-order model, demonstrated that the adsorption process indicated a complex multi-adsorption process. Meanwhile, the adsorption also fit to Langmuir and Sips models, suggesting monolayer-level adsorption with heterogeneous sites located on S-mZVI bm . The S-mZVI bm could enhance Cr(VI) adsorption through various synergistic mechanisms, such as electrostatic interaction, chemical precipitation, surface complexation, and reduction. Overall, this research presented an innovative perspective for the modification of ZVI, and S-mZVI bm could be widely applied in the practical remediation of wastewater containing Cr(VI).