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As carbon dioxide (CO₂) is one of the main contributors to global warming and climate change, CO₂ mitigation technologies have been developed to alleviate CO₂ emissions. Among CO₂ capture and utilization techniques, microbial electrosynthesis (MES) has been regarded as a promising and cost-effective approach to contribute to global carbon neutrality via valorizing CO₂ into valuable biofuels and bioproducts in the context of circular bioeconomy. In this chapter, we first introduce the fundamentals of MES, followed by specific discussions on various products generated using the MES system (e.g., acetate, biomethane, alcohols, carboxylic acids, and bioplastics). The impact of different electrode materials (e.g., carbonaceous, metallic, and composite electrodes) on the MES performance is also discussed. Future perspectives and technological challenges in the development of MES systems are presented in the …