Bioelectrochemical treatment system (BET) with anoxic anodic microenvironment was studied with chemical wastewater (CW) in comparison with anoxic treatment (AxT, sequencing batch reactor (SBR)) with same parent anaerobic consortia. BET system documented relatively higher treatment efficiency at higher organic load (5.0 kg COD/m(3)) accounting for COD removal efficiency of (90%) along with nitrate (48%), phosphate (51%), sulphates (68%), colour (63%) and turbidity (90%) removal, compared to AxT operation (COD, 47%; nitrate, 36%; phosphate, 32%; sulphate, 35%; colour, 45% and turbidity, 54%). The self-induced bio-potential developed due to the electrode assembly in BET resulted in effective treatment with simultaneous bioelectricity generation (631 mA/m(2)). AxT operation showed persistent reduction behaviour, while simultaneous redox behaviour was observed with BET indicating balanced electron transfer. BET operation illustrated higher wastewater toxicity reduction compared to the AxT system which documents the variation in bio-electrocatalytic behaviour of same consortia under different microenvironment. (C) 2013 Elsevier Ltd. All rights reserved.