Fe(II) redox chemistry is a pivotal process of biogeochemical Fe cycle and the transformation of organic pollutants in subsurface aquifers, while its interfacial reactivity on iron oxides with varying surface chemistries remains largely unexplored. In this study, the redox processes of Fe(II) on two hematite with highly exposed {001} and {110} facets and their impacts on the transformation of nitrobenzene were investigated. Results suggest that Fe(II) adsorption is the rate-limiting step of the redox chain reactions, controlling the reduction potential (E). Nitrobenzene activates the facet electron transfer on hematite, leading to nitrobenzene reduction and Fe(II) oxidation. Moreover, {001} facet exhibits a higher reactivity and electron transport efficiency than {110} facet, which is attributed to a lower site density (0.809 #Fe/nm) and a lower E of hematite {001} facet than that of {110} facet. It is worth noting that the facet-dependent reduction activity is more intense at low pH or high Fe(II) activity. A slight dissolution of {110} facet was observed, indicating hematite {001} facet exhibits higher thermodynamic stability than {110} facet. This study confirms the facet-dependent reducing activity of surface bound Fe(II) on hematite, providing a new perspective for in-depth understanding of the interfacial reactions on hematite. The findings of this work broaden the biogeochemical process of Fe cycle in subsurface environments and its impact on the fate of organic pollutants in groundwater.