Carbon dioxide (CO2) is a widespread carbon resource on the earth. The biological conversion of CO2 into organic compounds is an important route for production of biofuels and bio-based chemicals. Owing to the insufficient energy supply and inefficient catalytic activities, the efficiency for biological CO2 fixation remains to be low. The electricity-driven reduction of CO2 using whole microorganisms, which termed as microbial electrosynthesis, provides a novel strategy for biological conversion of CO2. This review summarizes recent advances on microbial electrosynthesis, which covers the microorganisms used for electrosynthesis, extracellular electron transfer, and selection of electrode materials. Furthermore, future challenges and prospects of microbial electrosynthesis were discussed.