Li metal batteries (LMBs) reveal great application prospect in next-generation energy storage, because of their high energy density and low electrochemical potential, especially when paired with elemental sulfur and oxygen cathodes. Complex interfacial reactions have long been a big concern because of the elusive formation/dissolution of Li metal at the solid–electrolyte interface (SEI) layer, which leads to battery degradation under practical operating conditions. To precisely track the reactions at the electrode/electrolyte interfaces, in the past ten years, high spatio–temporal resolution, in situ electrochemical transmission electron microscopy (EC-TEM) has been developed. A preliminary understanding of the structural and chemical variation of Li metal during nucleation/growth and SEI layer formation has been obtained. In this perspective, we give a brief introduction of liquid cell development. Then, we comparably discuss the different configurations of EC-TEM based on open-cell and liquid-cell, and focus on the recent advances of liquid-cell EC-TEM and its investigation in the electrodes, electrolytes, and SEI. Finally, we present a perspective of liquid-cell EC-TEM for future LMB research.