<P><B>Abstract</B></P> <P>Electro-biocatalytic reactor was operated using selectively enriched mixed culture biofilm for about 320 days with CO<SUB>2</SUB>/bicarbonate as C-source. Biocathode consumed higher current (−16.2 ± 0.3 A/m<SUP>2</SUP>) for bicarbonate transformation yielding high product synthesis (0.74 g/l/day) compared to CO<SUB>2</SUB> (−9.5 ± 2.8 A/m<SUP>2</SUP>; 0.41 g/l/day). Product slate includes butanol and butyric acid when CO<SUB>2</SUB> gets transformed but propionic acid replaced both when bicarbonate gets transformed. Based on electroanalysis, the electron transfer might be H<SUB>2</SUB> mediated along with direct transfer under bicarbonate turnover conditions, while it was restricted to direct under CO<SUB>2</SUB>. Efficiency and stability of biofilm was tested by removing the planktonic cells, and also confirmed in terms of Coulombic (85–97%) and carbon conversion efficiencies (42–48%) along with production rate (1.2–1.7 kg/m<SUP>2</SUP> electrode) using bicarbonate as substrate. Selective enrichment of microbes and their growth as biofilm along with soluble CO<SUB>2</SUB> have helped in efficient transformation of CO<SUB>2</SUB> up to C4 organic molecules.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Electro-biocatalytic CO<SUB>2</SUB> transformation to organics was studied for 320 days. </LI> <LI> Stabilized biocathode of selectively enriched culture was studied for electro-synthesis. </LI> <LI> CO<SUB>2</SUB> availability in soluble form dictated the product slate. </LI> <LI> Electron transfer is possibly H<SUB>2</SUB> mediated and DET with bicarbonate but restricted to DET with CO<SUB>2</SUB>. </LI> <LI> CE was high irrespective of carbon nature but CCE significantly varied for CO<SUB>2</SUB> and bicarbonate. </LI> </UL> </P>