Biocatalyst behavior was comparatively evaluated under diverse microenvironments viz., self-induced electrogenic (bioelectrochemical treatment, BET) and anaerobic treatment (AnT) microenvironments, with real-field pharmaceutical wastewater. Relatively higher treatment efficiency was observed with BET (COD removal, 78.70%) over AnT (32%) along with the power output. Voltammetric profiles of AnT showed persistent reduction behavior, while BET depicted simultaneous redox behavior. BET operation documented significantly higher bio-electrocatalytic activity (k app, 245.22s -1) than AnT (k app, 7.35s -1). The electron accepting conditions due to the presence of electrode in the BET might contributed to higher electrogenesis leading to enhanced substrate degradation along with the removal of multiple pollutants accounting for the effective reduction of toxicity levels of wastewater. Even at higher organic loads, BET operation showed good treatment efficiency without process inhibition. Introduction of electrode-membrane assembly in anaerobic microenvironment showed significant change in the electrocatalytic behavior of biocatalyst resulting in enhanced treatment of complex wastewater. © 2011 Elsevier Ltd.