Solid-state electrolytes are a promising family of materials for the next generation of high-energy rechargeable lithium batteries. Polymer electrolytes (PEs) have been widely investigated due to their main advantages, which include easy processability, high safety, good mechanical flexibility, and low weight. This review presents recent scientific advances in the design of versatile polymer-based electrolytes and composite electrolytes, underlining the current limitations and remaining challenges while highlighting their technical accomplishments. The recent advances in PEs as a promising application in structural batteries are also emphasized.