A UV-light polymerized three-dimensional (3D) network gel polymer electrolyte (GPE) is designed and fabricated for solid-state lithium-sulfur (Li-S) batteries. The GPE exhibits wide electrochemical window up to 5.05 V (vs. Li+/Li), outstanding thermostability and mechanical property. Besides, the GPE effectively suppresses the extension of lithium dendrite and the electron-donating groups in GPE inhibit the shuttle of lithium polysulfides. The assembled solid-state Li-S batteries with the 3D network GPE show high specific capacity retention of 69.1% after 300 cycles at 0.5 C. With the consideration of these, the GPE in this report undoubtedly provides an effective technique to design high performance solid-state Li-S batteries.