Microbial Electrosynthesis (MES) has been widely applied for acetic acid (HA) production from CO₂ and electricity. Ethanol (EtOH) has a higher market value than HA, and wide application in industry and as a biofuel. However, it has only been obtained sporadically and at low concentrations, probably due to sub-optimal operating conditions. This study aimed at enhancing EtOH productivity in MES cells by jointly optimising key operation parameters, including pH, H₂ and CO₂ partial pressure (pH₂ and pCO₂), and HA concentration, to promote solventogenesis. Two H-type cells were operated in fed-batch mode at −0.8 V vs. SHE with CO₂ as the sole carbon source. A mixed culture, enriched with Clostridium ljungdahlii was used as the biocatalyst. The combination of low pH (<4.5) and pCO₂ (<0.3 atm), along with high HA concentration (about 6 g L⁻¹) and pH₂ (>3 atm), were mandatory conditions for maintaining an efficient solventogenic culture, dominated by Clostridium sp., capable of high-rate EtOH production. The maximum EtOH production rate was 10.95 g m⁻² d⁻¹, and a concentration of 5.28 g L⁻¹ was achieved. Up to 30 % of the electrons and 15.2 % of the carbon provided were directed towards EtOH production, and 28.1 kWh were required for the synthesis of 1 kg of EtOH from CO₂. These results highlight that strict conditions are required for a continuous, reliable, EtOH production in MES cells. Future investigation should focus on improving cell configuration to achieve EtOH production at higher current densities while minimizing the electric energy input.