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This review develops a mechanism\u2013interface\u2013function\u2013readiness framework that connects extracellular electron transfer (EET) with biofilm ecology, microbiome\u2013electrode organisation, environmental process performance, and translational maturity. Direct transfer through multiheme cytochromes and conductive structures, mediated transfer through soluble redox shuttles, and interspecies electron transfer are evaluated as system\u2010dependent pathways rather than universally ranked mechanisms. Particular emphasis is placed on wastewater treatment and resource recovery, anaerobic digestion, pollutant and metal transformation, soil and sediment bioelectrochemistry, carbon conversion, microbial fuel cells, microbial electrolysis cells, electro\u2010fermentation, and microbial electrosynthesis. 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