AbstractSolid‐state electrolytes (SSEs) are recognized as attractive candidates to realize safe and high‐energy‐density lithium metal batteries (LMBs). However, the practical application of SSEs still faces challenges such as insufficient room‐temperature ionic conductivity, unsatisfactory mechanical properties, and large internal resistance. Extensive research efforts have been made to explore new electrochemistry and technologies to address those challenges. Among them, the construction of order‐structured SSEs has emerged as a promising strategy. The anisotropic behavior induced by the orientation offers SSEs with desired properties targeting specific functions, and therefore the rational design of the order‐structured SSE provides an alternative solution to achieve an ideal SSE. This review discusses the structure‐property correlation of SSEs, and then summarizes the design strategies to construct order‐structured SSEs. Finally, the current challenges and possible future research directions for order‐structured SSEs for scalable high‐energy‐density LMBs are presented.