Persulfate (S₂O₈²⁻; PS) has been used with zerovalent iron (ZVI) for the remediation of various contaminants. However, the passive layer of commercial ZVI limitates the corrosion of ZVI and reaction with PS. In our initial attempt, we mechanically combined Na₂S₂O₈ and micro-sized ZVI by simple ball milling to improve the reaction of PS and ZVI. The synthesized composite (PSZVI^bm) was compared to the system in which Na₂S₂O₈ was separately injected with ball-milled ZVI (ZVI^bm/PS). The reaction in ZVI^bm/PS depended on surface-bound Fe(II) to initiate PS consumption. Conversely, the PS immediately destroyed the passive layer and enhanced the corrosion of ZVI in PSZVI^bm. Therefore, PSZVI^bm reduced nitrobenzene rapidly with higher efficiency in deionized water (94.2%) compared to that of ZVI^bm/PS (73.1%). Furthermore, PSZVI^bm was less affected by the real groundwater matrix and removed nitrobenzene with higher efficiency (64.7%) than ZVI^bm/PS (10.3%). Due to the different PS consumption rates and radical species, PSZVI^bm removed phenol with lower efficiency (22.7%) than ZVI^bm/PS (61.5%), showing the different effects of surface-bound Na₂S₂O₈ on the reduction/oxidation capacities of ZVI. This study suggests a new scalable method to control the reactivity of ZVI without the use of toxic chemicals and wastewater generation.