At present, replacing the liquid electrolyte in a lithium metal battery with a solid electrolyte is considered to be one of the most powerful strategies to avoid potential safety hazards. Composite solid electrolytes (CPEs) have excellent ionic conductivity and flexibility owing to the combination of functional inorganic materials and polymer solid electrolytes (SPEs). Nevertheless, the ionic conductivity of CPEs is still lower than those of commercial liquid electrolytes, so the development of high-performance CPEs has important practical significance. Herein, a novel fast lithium-ion conductor material LiTa2PO8 was first filled into poly(ethylene oxide) (PEO)-based SPE, and the optimal ionic conductivity was achieved by filling different concentrations (the ionic conductivity is 4.61 x 10(-4) S/cm with a filling content of 15 wt% at 60 degrees C). The enhancement in ionic conductivity is due to the improvement of PEO chain movement and the promotion of LiTFSI dissociation by LiTa2PO8. In addition, LiTa2PO8 also takes the key in enhancing the mechanical strength and thermal stability of CPEs. The assembled LiFePO4 solid-state lithium metal battery displays better rate performance (the specific capacities are as high as 157.3, 152, 142.6, 105 and 53.1 mAh/g under 0.1, 0.2, 0.5, 1 and 2 C at 60 degrees C, respectively) and higher cycle performance (the capacity retention rate is 86.5% after 200 cycles at 0.5 C and 60 degrees C). This research demonstrates the feasibility of LiTa2PO8 as a filler to improve the performance of CPEs, which may provide a fresh platform for developing more advanced solid-state electrolytes. (C) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.