Solid electrolytes with superb performances, including high ionic conductivity, wide electrochemical window, and optimal compatibility with a lithium (Li) metal anode, would be an efficient solution to the development of nextgeneration high-energy-density Li ion batteries. Herein, a novel polycarbonatebased gel polymer electrolyte (PCPVC-GPE) with high Li + conductivity up to 3.43 mS cm −1 at room temperature is reported. The PCPVC-GPE is synthesized via ringopening metathesis polymerization and thiol−ene "click" chemistry from norbornene derivative monomer exhibiting a high electrochemical oxidation voltage (5.2 V) and superior compatibility with a Li metal anode. A Li/PCPVC-GPE/Li symmetrical cell delivers good cycling stability for 1900 h. As a proof of concept, an assembled Li/PCPVC-GPE/LiFePO 4 cell has a large capacity of 129.4 mAh g −1 at 0.5 C and high capacity retention of 77.1% at 3.0 C after 1000 cycles. All results indicate that PCPVC-GPE could be employed as a promising polymer electrolyte for the advanced solid Li metal batteries.