Electrosynthesis of multi-carbon compounds from the carbon dioxide present in biogas is a nascent approach towards purification of biogas. Microbial electrosynthesis (MES) cells, fabricated using different electrode materials, were operated using different electrolytes and mixed anaerobic culture as biocatalysts in the cathodic chamber under an applied cathode potential of −0.7 V vs standard hydrogen electrode (SHE). The rate of production of acetate, isobutyrate, propionate and 2-piperidinone from reduction of CO2 in the cathodic chamber of the MES was 0.81 mM/day, 0.63 mM/day, 0.44 mM/day and 0.53 mM/day, respectively. As methane was also present in the biogas, methyl derivatives of these acids were also found in traces in catholyte. It was observed that the use of nickel foam as an anode, 1 M NiSO4 solution as anolyte, graphite felt as a cathode, phosphate buffer solution as catholyte at a pH of 5.2 proved to be the best possible combination for MES for this study to get enhanced product yield at higher energy efficiency.