Microbial catalyzed electrochemical systems (MCES) have been intensively pursued in both basic and applied research as a futuristic and sustainable platform specifically in harnessing energy and generating value added bio-products. MCES have documented multiple/diverse applications which include microbial fuel cell (for harnessing bioelectricity), bioelectrochemical treatment system (waste remediation), bioelectrochemical system (bio-electrosynthesis of various value added products) and microbial electrolytic cell (H2 production at lower applied potential). Microorganisms function as biocatalyst in these fuel cell systems and the resulting electron flux from metabolism plays pivotal role in bio-electrogenesis. Exo-electron transfer machineries and strategies that regulate metabolic flux towards exo-electron transport were delineated. This review addresses the contemporary progress and advances made in MCES, focusing on its application towards value addition and waste remediation. © 2014 Elsevier Ltd.