Increasing carbon footprint alters the carbon balance in nature, thereby worsening global climate change. The conversion of carbon dioxide (CO2) into value-added products through biological routes is the pathway of the future because of its ecological and sustainable character. The present study evaluated the conversion of CO2 into short-chain fatty acids (SCFA)/volatile fatty acids (VFA) and methane using four experimental conditions (R1-R4). The experimental conditions are R1 was an anaerobic fermenter (AF) operated as control, R2 consisted of an AF with electrodes operated in open circuit, R3 was an AF with electrodes operated in a closed circuit with 100 Ω as load and R4 was an electro-fermentation reactor with an applied cathodic potential of −0.8 V vs. Ag/AgCl. The results were assessed in terms of production of SCFA, methane, current density and inorganic carbon reduction. Electro-fermentation (R4) setup achieved the highest production of SCFA (2050 mg/L) and methane (41.2 mL/day) compared to other reactors. R3 reported 1800 mg/L and 24 mL/day, R2 reported 1560 mg/L and 15 mL/day and R1 reported 1430 mg/L and 10 mL/day of methane and SCFA production. The study-inferred that electro-fermentation could effectively catalyse the biochemical reactions and enhance the conversion of CO2 to organic compounds in a sustainable manner.