Waste biomass is a cheap and relatively abundant source of electrons for microbes capable of producing electrical current outside the cell. Rapidly developing microbial electrochemical technologies, such as microbial fuel cells, are part of a diverse platform of future sustainable energy and chemical production technologies. We review the key advances that will enable the use of exoelectrogenic microorganisms to generate biofuels, hydrogen gas, methane, and other valuable inorganic and organic chemicals. Moreover, we examine the key challenges for implementing these systems and compare them to similar renewable energy technologies. Although commercial development is already underway in several different applications, ranging from wastewater treatment to industrial chemical production, further research is needed regarding efficiency, scalability, system lifetimes, and reliability.