Dissimilatory Fe(III) reduction represents a fundamental microbial respiratory process in anoxic soils and sediments, exerting profound influence on the biogeochemical cycling of iron, carbon, and sulfur. In recent years, accumulating evidence has revealed that under specific environmental conditions, metabolically active archaea can outnumber bacteria in certain soil ecosystems, indicating their non-negligible contribution to global C and N cycling. Compared with bacteria, however, the study of Fe(III)-reducing archaea remains in its infancy. Existing research has demonstrated that these archaea are capable of utilizing Fe(III) (hydr)oxides as terminal electron acceptors for anaerobic respiration via both direct and indirect electron transfer pathways. This review provides a comprehensive overview of the diversity of Fe(III)-reducing archaea and their distinctive extracellular electron transfer (EET) mechanisms. Direct EET appears primarily reliant on multiheme c-type cytochromes, but may also involve archaea-specific key components such as molybdopterin oxidoreductases (MoOR), heterodisulfide reductases (HdrDE), and methanophenazines (MP). Indirect pathways may involve the secretion of yet-unidentified endogenous electron shuttles or the utilization of exogenous redox mediators that facilitate long-range electron transfer to extracellular Fe(III) oxides. Distinct archaeal groups, including hyperthermophiles, methanogens, and anaerobic methanotrophic archaea (ANME), exhibit remarkable variation in substrate utilization, electron acceptor preference, and ecological distribution. These differences reflect both the metabolic versatility and evolutionary innovation of archaeal electron transfer systems. Despite these advances, mechanistic understanding of archaeal Fe(III) reduction remains limited, largely due to challenges in cultivation and genetic manipulation. Future research should prioritize the development of efficient archaeal genetic systems, the establishment of genetically tractable model organisms to uncover novel uncultivated Fe(III)-reducing archaeal taxa. Analyzing the molecular mechanisms and ecological roles of archaeal Fe(III) reduction will provide critical insights into the evolutionary diversification of microbial respiration and the functioning of redox processes in natural ecosystems. Moreover, quantifying the ecological impact of these archaea in global Fe-C coupling will enhance our understanding of nutrient dynamics and redox regulation in soils and sediments. Ultimately, these efforts will contribute to a more comprehensive and mechanistic model of archaeal participation in Earth’s biogeochemical networks.