Poly(ethylene oxide) (PEO) is one of the most promising candidates in polymer solid‐state electrolyte. However, the polymer matrix has a high degree of crystallinity and thus manifests low conductivity, which restricts its application in all solid‐state lithium‐ion battery. Herein, a new composite polymer electrolyte (PLWLS), which is comprised of PEO, LiClO4, and the independently synthetized walnut‐like SiO2 (WLS) as nano‐fillers, is designed and prepared by the tape‐casting way. The optimum mass fraction of walnut‐like SiO2 is determined by physical and electrochemical characterization. The result shows that the PLWLS‐15 with 15 wt % walnut‐like SiO2 nanoparticles has a crystallinity of 13.7%. Similarly, the maximum tensile strength is improved greatly. The assembled all‐solid‐state lithium‐ion battery with LiFePO4/PLWLS‐15/Li exhibits a higher discharge capacity of 167 mAh g−1 at 0.1 C (1C = 170 mAh g−1) and 143 mAh g−1 at 0.5 C in first cycle, lower voltage polarization and better cycle performance. Therefore, adding nanoparticle into PEO‐based solid‐state electrolyte could effectively promote the mechanical property and electrochemical performance, and thus provide a possibility of application for PLWLS‐15 in next generation all solid‐state lithium battery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48810.