Li‐ions battery is widely used and recognized, but its energy density based on organic electrolytes has approached the theoretical upper limit, while the use of organic electrolytes also brings some safety hazards (leakage and flammability). Polymer electrolytes (PEs) are expected to fundamentally solve the safety problem and improve energy density. Therefore, Li‐ions battery based on solid PE has become a research hotspot in recent years. However, low ionic conductivity and poor mechanical properties, as well as a narrow electrochemical window limit its further development. Dendritic PEs with unique topology structure has low crystallinity, high segmental mobility, and reduced chain entanglement, providing a new avenue for designing high‐performance PEs. In this review, the basic concept and synthetic chemistry of dendritic polymers are first introduced. Then, this story will turn to how to balance the mechanical properties, ionic conductivity, and electrochemical stability of dendritic PEs from synthetic chemistry. In addition, accomplishments on dendritic PEs based on different synthesis strategies and recent advances in battery applications are summarized and discussed. Subsequently, the ionic transport mechanism and interfacial interaction are deeply analyzed. In the end, the challenges and prospects are outlined to promote further development in this booming field.