PEO is one of the common composite polymer electrolyte vehicles; however, the presence of crystalline phase at room temperature, high interface impedance, and low oxidation resistance (<4.0 V) limit its application in stable all-solid-state lithium metal batteries. Herein, we designed a PEO-based solid polymer electrolyte (SPE) by adding boehmite nanoparticles to address the above-mentioned issues. Different-grain-sized boehmite nanoparticles were synthesized by adjusting the hydrothermal temperature. Moreover, the impacts of these distinct grain-sized boehmite nanoparticles used to fabricate boehmite/PEO polymer electrolytes (BPEs) on the performance of all-solid-state lithium metal batteries were investigated. It was found that with the increase in boehmite's grain size, BPEs show better performance. The best BPE exhibited an improved Li