Chlorophenols (CPs) are a class of synthetic organic chemicals that are widely distributed in soil and groundwater, posing significant risks to human health and the environment due to persistence, acute toxicity, and potential carcinogenicity. Zero-valent iron (ZVI) has emerged as a promising remediation technique for CPs, but its efficacy is often hindered by surface passivation, non-target competition, and limited mobility in the subsurface. While CPs are inherently biodegradable, their high toxicity and the lack of functional enzymes in indigenous microbial systems restrict the effectiveness of bioremediation. Recently, a hybrid system integrating ZVI with microbial degradation draws increasingly research interests, paving out a new path for sustainable degradation of CPs. These systems leverage the synergistic interactions between ZVI and microorganisms to enhance CP biodegradation. This review provides a comprehensive analysis of the advancement. Key topics include the enhancement of electron transfer, alterations to microbial communities, mitigation of toxicity, and the interplay between other processes. Operation modes, ZVI dosage, and interactions with naturally occurring iron minerals, are also discussed in the context of applications in soil and groundwater remediation. Despite research efforts and successful implementations, critical knowledge gaps remain, particularly in regard to the characterization of microbial processes in natural systems, highlighting the need for future research.