We employed the environmentally friendly TOCN coupling the soft polymer electrolyte to develop a new solid-state polymer electrolyte (SPE) with enhanced compressive strength by simple solution casting. We showed that our prepared SPEs showed decent electrochemical stability for more than 1000 hours in the assembled lithium symmetric battery at a current density of 0.15 mA/cm2. Furthermore, the assembled LiFePO4 battery can deliver a specific capacity of 160 mAh/g at 0.1C, and maintain high Coulombic efficiency and 72％ of discharge capacity retention efficiency after long-term cycles. Our developed SPEs not only possess high eco-friendly sustainability but also show the promising potential for realizing safe and stable Li-metal batteries.