AbstractSolid polymer electrolytes (SPEs) are still being considered as a candidate to replace liquid electrolytes for high‐safety and flexible lithium batteries due to their superiorities including light‐weight, good flexibility, and shape versatility. However, inefficient ion transportation of linear polymer electrolytes is still the biggest challenge. To improve ion transport capacity, developing novel polymer electrolytes are supposed to be an effective strategy. Nonlinear topological structures such as hyperbranched, star‐shaped, comb‐like, and brush‐like types have highly branched features. Compared with linear polymer electrolytes, topological polymer electrolytes possess more functional groups, lower crystallization, glass transition temperature, and better solubility. Especially, a large number of functional groups are beneficial to dissociation of lithium salt for improving the ion conductivity. Furthermore, topological polymers have strong design ability to meet the requirements of comprehensive performances of SPEs. In this review, the recent development in topological polymer electrolytes is summarized and their design thought is analyzed. Outlooks are also provided for the development of future SPEs. It is expected that this review can raise a strong interest in the structural design of advanced polymer electrolyte, which can give inspirations for future research on novel SPEs and promote the development of next‐generation high‐safety flexible energy storage devices.