Real-field acidogenic effluents rich in short chain carboxylic acids/volatile fatty acids (VFA) were obtained from biohydrogen (H-2) producing reactor operated with spent wash as substrate. A single chambered microbial electrolysis cell (MEC) was designed to electro ferment the effluents towards additional H-2 production with simultaneous treatment using acid pretreated biocatalyst. The effect of VFA concentration (4000 mg/l and 8000 mg/l) on biohydrogen production with simultaneous remediation was studied at 0.2 V and 0.6 V applied potential along with closed circuit (CC) and control operations. Maximum cumulative H-2 production (CHP) and hydrogen production rate (HPR) of 39.35 ml and 0.057 mmol/h was observed at 0.6 V. VFA utilization as substrate was high at 0.6 V (68%) followed by 0.2 V (45%), CC (39%) and control (19%). Dehydrogenase activity, pH profiles, low redox slopes (beta(a) and beta(c)) and polarization resistance (R-p) at 0.6 V corroborated well with the H-2 production at both the VFA concentrations operated. Additional H-2 recovery utilizing VFA rich effluents demonstrates the sustainability of this integrated approach through electro fermentation in a single chamber MEC. (C) 2015 Elsevier B.V. All rights reserved.