Combining the sector of electric power storage and utilization and the sector of (bio)chemical production is of paramount importance for a future biobased economy. When carbon dioxide (CO2) is to be exploited as feedstock, the use of electric energy can be a prime option for its utilization. Microorganisms that reduce CO2 utilizing electrons “fed” by electrodes are considered as electroactive microorganisms and can be specified as electroautotrophs. In this chapter, we provide an overview on electroautotrophs and how their lifestyle can be classified. Subsequently, a brief overview on the state of the art of microbial electrosynthesis by electroautotrophic microorganisms as well as microbiomes and the currently realized products and their yields is provided. Further, the combined abiotic electrochemical CO2 reduction to C1-building blocks (e.g., formate) and the subsequent utilization of the gained product for biosynthesis is highlighted as a promising alternative approach. Finally, the integration of microbial electrosynthesis from CO2 in the overarching concept of electrobiorefineries is illustrated.