Risks associated with climate change are driving the search for new technologies to produce fuels and chemicals. The microbial electrosynthesis of chemical compounds, using electricity and CO2 as feedstock and microbes to deliver the catalysts, has the potential to be one of those technologies. Central to the production of multicarbon compounds by this process is the bioelectrosynthesis of acetate (electroacetogenesis), and significant improvements in productivity and insightful discoveries concerning the extracellular transfer of electrons to the acetogenic microorganisms have been made recently. This review examines these advances and how they are influencing the development of microbial electrosynthesis into a new biotechnology for the sustainable production of fuels and chemicals.