Microbial electrosynthesis (MES) is a promising carbon utilization technology, but the low-value products (i.e., acetate or methane) and the high electric power demand hinder its industrial adoption. In this study, electrically efficient MES cells with a low ohmic resistance of 15.7 mΩ m2 were operated galvanostatically in fed-batch mode, alternating periods of high CO2 and H2 availability. This promoted acetic acid and ethanol production, ultimately triggering selective (78% on a carbon basis) butyric acid production via chain elongation. An average production rate of 14.5 g m−2 d−1 was obtained at an applied current of 1.0 or 1.5 mA cm−2, being Megasphaera sp. the key chain elongating player. Inoculating a second cell with the catholyte containing the enriched community resulted in butyric acid production at the same rate as the previous cell, but the lag phase was reduced by 82%. Furthermore, interrupting the CO2 feeding and setting a constant pH2 of 1.7–1.8 atm in the cathode compartment triggered solventogenic butanol production at a pH below 4.8. The efficient cell design resulted in average cell voltages of 2.6–2.8 V and a remarkably low electric energy requirement of 34.6 kWhel kg−1 of butyric acid produced, despite coulombic efficiencies being restricted to 45% due to the cross-over of O2 and H2 through the membrane. In conclusion, this study revealed the optimal operating conditions to achieve energy-efficient butyric acid production from CO2 and suggested a strategy to further upgrade it to valuable butanol.