Mixed culture of sulphate reducing bacteria named TERI-MS-003 was used for development of biocathode on activated carbon fabric fastened to stainless steel mesh for conversion of volatile fatty acids to reduced organic compounds under chronoamperometric conditions of -0.85 V vs. Ag/AgCl (3.5 M KCl). A range of chemicals were bioelectrosynthesized, however the gases present in headspace environment of the bioelectrochemical reactor governed the product profile. Succinate, ethanol, hydrogen, glycerol and propionate were observed to be the predominant products when the reactor was hermetically sealed. On the other hand, acetone, propionate, isopropanol, propanol, isobutyrate, isovalerate and heptanoate were the predominant products when the reactor was continuously sparged with nitrogen. This study highlights the importance of head space composition in order to manoeuvre the final product profile desired during a microbial electro-synthesis operation and the need for simultaneously developing effective separation and recovery strategies from an economical and practical standpoint. (C) 2014 Elsevier Ltd. All rights reserved.