Liquid crystal has the advantages of both solid and liquid. As a battery electrolyte material, it has attracted more and more attention and research for safety, ion transfer rate, processability, electrochemical stability and interface compatibility. Thermotropic liquid crystal materials can construct complete one-dimensional, two-dimensional or three-dimensional ion transport channels through self-assembly, which is a field of widespread concern in electrolyte research. In particular, the stable two-dimensional ion transport channels constructed by smectic liquid crystalline electrolytes have received extensive attention. Compared with other liquid crystalline electrolytes such as columnar phase, bicontinuous cubic phase or ionic liquid crystals, smectic phase has obvious advantages in ion transfer rate. In this paper, the origin, development and structural characteristics of thermotropic liquid crystal materials as ion battery electrolytes are reviewed, and the research progress and application status at home and abroad in recent years are introduced in details.