Decarbonisation of the economy has become a priority at the global level, and the resulting legislative pressure is pushing the chemical and energy industries away from fossil fuels. Microbial electrosynthesis (MES) has emerged as a promising technology to promote this transition, which will further benefit from the decreasing cost of renewable energy. However, several technological challenges need to be addressed before the MES technology can reach its maturity. The aim of this review is to critically discuss the bottlenecks hampering the industrial adoption of MES, considering the whole production process (from the CO2 source to the marketable products), and indicate future directions. A flexible stack design, with flat or tubular MES modules and direct CO2 supply, is required for site-specific decentralised applications. The experience gained for scaling-up electrochemical cells (e.g. electrolysers) can serve as a guideline for realising pilot MES stacks to be technologically and economically evaluated in industrially relevant conditions. Maximising CO2 abatement rate by targeting high-rate production of acetate can promote adoption of MES technology in the short term. However, the development of a replicable and robust strategy for production and in-line extraction of higher-value products (e.g. caproic acid and hexanol) at the cathode, and meaningful exploitation of the currently overlooked anodic reactions, can further boost MES cost-effectiveness. Furthermore, the use of energy storage and smart electronics can alleviate the fluctuations of renewable energy supply. Despite the unresolved challenges, the flexible MES technology can be applied to decarbonise flue gas from different sources, to upgrade industrial and wastewater treatment plants, and to produce a wide array of green and sustainable chemicals. The combination of these benefits can support the industrial adoption of MES over competing technologies.