Most modification strategies of polyethylene oxide (PEO)‐based solid polymer electrolyte focus on improving the room temperature ionic conductivity, while disregarding its inherent flammability that poses substantial safety hazard. Herein, a self‐extinguishing quasi‐solid‐state polymer electrolyte (PTTF‐SPE), which combines excellent room temperature electrochemical properties and high safety, has been developed by introducing triethyl phosphate (TEP) as a low‐cost and highly effective flame retardant. The cross‐linking structure derived from ‐CH2‐CH2‐O‐ segments of tetramethylene glycol dimethyl ether (TEGDME) and PEO makes a contribution to a high amorphous state of polymer. A robust solid electrolyte interphase (SEI) formed by preferential decomposition of fluoroethylene carbonate (FEC) that acts as a film‐forming additive, which can prevent TEP from degradation at lithium metal anode. The optimized PTTF‐SPE exhibits high ionic conductivity (0.54×10‐3 S/cm) and lithium transference number (0.71) at room temperature. The LiFePO4||Li battery demonstrates excellent cycle life over 500 cycles at 0.5 C with a high average discharge capacity of 131 mAh/g. A symmetric Li||Li battery that operating for 850 hours indicates a good compatibility of PTTF‐SPE towards lithium metal. This work provides a new idea for developing high‐energy‐density and high‐safety lithium‐metal batteries (LMBs) for room temperature.