Given the aggravated greenhouse effect caused by CO2 and the current energy shortage, CO2 capture and reuse has been gaining ever-increasing concerns. Microbial Electrolysis Cells (MECs) has been considered to be a promising alternative to recycle CO2 bioelectrochemically to low-carbon electrofuels such as CH4 by combining electroactive microorganisms with electrochemical stimulation, enabling both CO2 fixation and energy recovery. In spite of the numerous efforts dedicated in this field in recent years, there are still many problems that hinder CO2 bioelectroconversion technique from the scaling-up and potential industrialization. This review comprehensively summarized the working principles, extracellular electron transfers behaviors, and the critical factors limiting the wide-spread utilization of CO2 electromethanogenesis. Various characterization and electrochemical testing methods for helping to uncover the underlying mechanisms in CO2 electromethanogenesis have been introduced. In addition, future research needs for pushing forward the development of MECs technology in real-world CO2 fixation and recycling were elaborated.