Recently, poly(ethylene oxide) (PEO)-based solid polymer electrolytes have been attracting great attention, and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all -solid-state lithium metal batteries. In this article, a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all -solid-state lithium metal batteries. The PEO-based composite electrolyte is fabricated by hot -pressing PEO, LiTFSI and Ti 3 C 2 T x MXene nanosheets into glass fiber cloth (GFC). The as -prepared GFC@PEO-MXene electrolyte shows high mechanical properties, good electrochemical stability, and high lithium -ion migration number, which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene. Such as, the GFC@PEO-1 wt% MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa, which are increased by 1205% and 6048% over those of PEO. Meanwhile, the ionic conductivity of GFC@PEO-1 wt% MXene at 60 degrees C reaches 5.01 x 10 -2 S m -1 , which is increased by around 200% compared with that of GFC@PEO electrolyte. In addition, the Li/Li symmetric battery based on GFC@PEO-1 wt% MXene electrolyte shows an excellent cycling stability over 800 h (0.3 mA cm -2 , 0.3 mAh cm -2 ), which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt% MXene electrolyte with Li anode. Furthermore, the solid-state Li/ LiFePO 4 battery with GFC@PEO-1 wt% MXene as electrolyte demonstrates a high capacity of 110.2 -166.1 mAh g -1 in a wide temperature range of 25 -60 degrees C, and an excellent capacity retention rate. The developed sandwich structured GFC@PEO-1 wt% MXene electrolyte with the excellent overall performance is promising for next generation high performance all -solid-state lithium metal batteries.