Developing all-solid-state lithium batteries has been one of the most effective methods to ensure safety for new energy devices, especially with flexible solid polymer electrolyte as a crucial component. However, the electrolyte exhibits low ionic conductivity at room temperature that obviously inhibits the progress of all-solid-state lithium batteries. In this study, we develop a few solid polymer electrolytes to enhance the lithium ion transport ability by using crosslinking polymer methods. The results show that adjustments of the cross-linked centers and branches of the polymer significantly improve the ionic conductivity of the electrolyte. Besides, all-solid-state lithium sulfur batteries with the solid electrolytes are studied. The morphology and structures at the electrode/electrolyte interfaces during the charge and discharge processes are investigated by FIB-SEM, EIS, FTIR and NMR. The effects of molecular structures of solid polymer electrolytes on ionic conductivity and interfacial compatibility are discussed.