A membrane-less anoxic bioelectrochemical treatment (AxBET) system was evaluated to study the influence of bioelectrogenic activity during the treatment of chemical wastewater (CW). Increment in power generation was observed with increase in substrate loading (61-204 mW/m2) indicating the ability of anodic bacteria in BET system to utilize the complex chemicals as the sole carbon source. Derivative analysis of voltammograms depicted by positive and negative peak potentials which relate to the extracellular electron transport sites (EETs) that presumably play a significant role in electron transfer. These self-driven redox mediators varied with respect to the substrate load. The microbial population was dominated by anaerobic microorganisms which are commonly involved in effluent treatment plants during the initial phase of operation. A gradual shift in the microbial community was observed towards enrichment of electrogenically active bacteria belonging to phyla viz., Firmicutes and Proteobacteria after prolonged operation. Shannon Index and principal component analysis correlated with the microbial profile studies. The feasibility of self-driven bioremediation of chemical wastewater in an AxBET system demonstrated bioelectricity production along with multipollutant removal simultaneously. © 2014 Elsevier Ltd.