The microbial catalyzed electrochemical reduction of CO2 is gaining significant attention in the field of energy and environment as it provides dual benefits of product recovery with simultaneous CO2 neutrality. Specific reduction of single carbon unit (C1-CO2) to two-carbon (C2-CH3COOH) carboxylic acids was studied in a bio-electrochemical system (BES) via a three stage experimental design using BESA treated and untreated (control) anaerobic consortia. During stage-I, enrichment of homoacetogenic culture was carried out by supplementing H-2 and CO2 in the reactors containing BESA treated and control cultures respectively. Optimization of pH was carried out in stage-II to enhance the carboxylic acids production at diverse pH range (acidic to alkaline viz., pH 5, 6.5, 8.5 and 10), where pH 10 was found to be optimum for maximum carboxylic acids (VFA: volatile fatty acids) generation in BESA treated (3500 mg/I) and control cultures (1200 mg/) respectively followed by pH 8.5 utilizing bicarbonate. Interestingly, reduction in VFA concentration was observed after 24 h which can be attributed to its consumption by other groups of bacteria that co-exist along with the enriched culture. During stage-III, bioelectrocatalytic production of acetate was evaluated by considering the optimized pH 10 and under applied potential of -0.8 V vs Ag/AgCl (S) in two BES viz., BESB (BES with BESA treated consortia) and BESC (BES with parent consortia as control) using CO2 and bicarbonate respectively. Maximum acetate production of 1.7 g/l (2.88 mmol/d)/2.1 g/l (3.55 mmol/d) was recovered in BESB through the bio-electrochemical reduction of CO2/bicarbonate, which correlated well with the observed higher reduction currents and columbic efficiency. (C) 2015 Elsevier Ltd. All rights reserved.