Abstract: A solid-state polymer electrolyte for lithium batteries is provided. The solid-state polymer electrolyte includes a solid-state network polymer electrolyte, formed by a modified poly(ethylene oxide) polymer material and an epoxy alkane crosslinking agent to form a poly(ethylene oxide) network structure, wherein the modified poly(ethylene oxide) high molecular weight material has an amino end, and the solid-state network polymer electrolyte comprises a lithium salt, The ratio of ethylene oxide (EO) to lithium (Li) in the solid-state network polymer electrolyte is 1:1 to 3:1, and a poly(vinylidene fluoride)-based polymer is doped in the solid-state network polymer electrolyte.