The use of gel polymer electrolytes (GPEs) is of great interest to build high-performing rechargeable lithium metal batteries (LMBs) owing to the combination of good electrochemical properties and improved safety. Herein, we report a facile and scalable one-pot preparation method of a GPE based on highly safe polyethylene glycol dimethyl ether (PEGDME) plasticizer in a poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) polymer matrix. The prepared GPE exhibits excellent safety (nonflammability and thermal stability up to 250 °C) and outstanding electrochemical properties at room temperature (high ionic conductivity of 3.4 × 10^–4 S cm^–1 and high lithium transference number). Moreover, high loading LiFePO₄ (6–7 mg cm^–2) LMB using such GPE delivers a good C-rate response and high capacity (ca. 1 mAh cm^–2 at C/10) with an excellent retention of 98% after 60 cycles in coin cell configuration. Notably, the prototype pouch cell (ca. 19 mAh at C/10) provides remarkable safety, mechanical flexibility, and strong tolerance toward bending and cutting. These results suggest that the prepared GPE is a promising candidate for the development of high performance, flexible, and safe LMBs that operate at room temperature, as well as for other energy storage systems beyond lithium-ion technologies.