Recycling CO2 into organic products through microbial electrosynthesis (MES) is attractive from the perspective of circular bioeconomy. However, several challenges need to be addressed before scaling-up MES systems. In this review, recent advances in electrode materials, microbe-catalyzed CO2 reduction and MES energy consumption are discussed in detail. Anode materials are briefly reviewed first, with several strategies proposed to reduce the energy input for electron generation and enhance MES bioeconomy. This was followed by discussions on MES cathode materials and configurations for enhanced chemolithoautotroph growth and CO2 reduction. Various chemolithoautotrophs, effective for CO2 reduction and diverse bioproduct formation, on MES cathode were also discussed. Finally, research efforts on developing cost-effective process for bioproduct extraction from MES are presented. Future perspectives to improve product formation and reduce energy cost are discussed to realize the application of the MES as a chemical production platform in the context of building a circular economy.