The objective of microbial electrosynthesis (MES) is to combine the advantages of electrochemistry and biotechnology in order to produce chemicals and fuels. This combination enables resource-efficient processes by using renewable raw materials and regenerative energies. In the last decade, different MES processes have been described, for example, MES based on biofilms or mediators, electro-fermentation, and secondary MES. This review compares the MES technologies with regard to the reached process performances in terms of key process indicators (i.e., coulombic efficiency (CE), product titre, productivity) and technology readiness level (TRL). Often the underlying mechanism of electron transfer in biofilm-based processes has not been elucidated and can therefore not be optimized. Similarly, technical aspects of electro-fermentation processes and processes with soluble mediators are under investigation and techno-economic assessments are missing. In contrast, the electrochemical production of microbial substrates in secondary MES or hybrid systems show high key process indicators and TRLs up to 7. In summary, the different types of MES processes offer options for today's industrial use, as well as an exciting and future-oriented technology that can be applied in a medium-term perspective.