Feasibility of integrating Microbial electrolysis cell (MEC) process with dark-fermentation process for additional hydrogen recovery as well as substrate degradation was demonstrated in the present study. MEC was employed in order to utilize the residual organic fraction present in the acidogenic effluents of dark fermentation process as substrate for hydrogen production with input of small electric current. MEC was operated at volatile fatty acids (VFA) concentration of 3000 mg/l under different poised potentials (0.2, 0.5, 0.6, 0.8 and 1.0 V) using anaerobic consortia as biocatalyst. Maximum hydrogen production rate (HPR), cumulative hydrogen production (CHP) (0.53 mmol/h and 3.6 mmol), dehydrogenase activity (1.65 mu g/ml) and VFA utilization (49.8%) was recorded at 0.6 V. Bio-electrochemical behavior of mixed consortia was evaluated using cyclic voltammetry and by Tafel slope analysis. Microbial diversity analysis using denaturing gradient gel electrophoresis confirmed the presence of gamma-proteobacteria (50%), Bacilli (25%) and Clostridia (25%). (C) 2013 Elsevier Ltd. All rights reserved.