Dehalococcoides (TCE) frequently persists in groundwater due to the inherent limitations of both abiotic and biotic remediation approaches. Nanoscale zero-valent iron (nZVI) enables rapid contaminant removal but is constrained by inefficient electron utilization, parasitic hydrogen evolution, and short reactive lifetimes. In contrast, organohalide-respiring bacteria, particularly Dehalococcoides mccartyi, can achieve complete detoxification to ethene, yet are limited by strict redox conditions and electron donor availability. Recent evidence suggests that nZVI–microbial systems function as a controllable “peak shaving–detoxification relay”, in which nZVI regulates electron flux and subsurface conditions, while microbial reductive dechlorination removes toxic intermediates such as cis-DCE and vinyl chloride. This review synthesizes advances in (i) electron transfer and allocation mechanisms; (ii) material design strategies for hydrogen regulation and electron selectivity; (iii) microbial interactions under nZVI-induced conditions; and (iv) engineering implementation from laboratory to field scale. Emphasis is placed on hydrogen management, system compatibility, and stability constraints. Overall, effective coupling relies on balancing electron flux and maintaining a sustainable reductive microenvironment rather than maximizing material reactivity. Future work should focus on defining operational windows and developing engineering control strategies for predictable groundwater remediation.



