The demand for higher energy density in energy storage devices drives further research on lithium metal batteries (LMBs) because of the high theoretical capacity and low voltage of lithium metal anode. Polymer electrolytes (PEs) exhibit obvious advantages in combating volatilization and leakage compared with liquid electrolytes, which improves the safety of LMBs. However, it is still difficult to construct PEs with a stable electrolyte-electrode interface for high-performance and long-term life LMBs. Herein, the gel polymer electrolyte (GPE-SL) containing deep eutectic electrolyte (DEE) and branchlike polymer skeleton are designed and prepared by the DEE-induced in situ cationic and radical polymerizations. The DEE provides a smooth Li+ migration pathway to ensure the electrochemical properties, and the multibrominated polymer matrix formed in situ enables a LiBr-rich solid electrolyte interphase (SEI) layer on lithium metal anode and prolongs the life span of LMBs. Hence, the Li|GPE-SL|LiFePO4 battery displays an excellent cycling stability with 84% capacity retention after 1200 cycles at 1C. This simple deep eutectic electrolyte-induced polymerization method provides a promising direction for high-performance LMBs with improved anode-electrolyte compatibility through the construction of a stable SEI layer in situ.