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Solid electrolyte is vital for solid-state lithium batteries with higher energy and power densities. In this work, we prepared a poly(ethylene oxide) (PEO)-LiClO₄–Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) composite solid electrolyte (CSE) membrane using a simple solution-casting method. It shows high Li ion conductivity (∼1 × 10^–3 S cm^–1) and excellent mechanical and electrochemical performances. All solid-state lithium batteries were fabricated with the CSE membrane of PEO-50 wt % LATP, Li metal anode, and LiFePO₄ cathode. By softening the CSE membrane at 80 °C, its ionic conductivity is improved, and the interfacial resistance of the prepared solid-state batteries is greatly reduced. The solid-state battery shows remarkable rate capability and excellent cycling performance. Even after 500 cycles, a capacity of 109.3 mAh g^–1 is still kept at 1C. Furthermore, the CSE membrane is used to assemble a flexible pouch cell …