To avoid the safety concerns of lithium−metal batteries (LMBs), which stem from the leaking of liquid electrolytes, solid polymer electrolytes (SPEs) are increasingly considered as alternative electrolytes. Carbon dioxide-derived poly(ethylene carbonate)-based SPE has drawn increasing attention due to its unique salt dissolution behavior, where the glass transition temperature (T g ) is reduced with increasing salt concentration. The limitations of the carbonate-based SPE are low mechanical strength and thermal decomposition induced by backbiting reaction at high temperatures, leading to unstable charge/discharge of LMBs. Accordingly, we prepared a cross-linked ethylene carbonated-based copolymer SPE filled with TiO 2 (CP-CPE) to achieve good thermal resistance and ionic conductivity simultaneously. The morphology observation, mechanical strength, thermal properties, and electrochemical performance of the CP-CPEs were investigated using scanning electron microscopy, tensile test, thermogravimetric analysis, differential scanning calorimetry, electrochemical impedance spectroscopy, linear sweep voltammetry, and galvanostatic charge/discharge tests. The surface morphology showed that the 5.0 wt % of TiO 2 is an appropriate amount that provided good filler dispersion for CP-CPE and gave the Young's modulus three-times higher than the ceramic-free CP-SPE. A CP-CPE incorporated with 5.0 wt % TiO 2 exhibits the highest ionic conductivity of 3.4 × 10 −5 S cm −1 at 60 °C, which was almost 10 times higher than that of the original cross-linked SPE without a filler (CP-SPE). The results also revealed that the 5.0 wt % CP-CPE promises to achieve a discharge capacity as high as 156 mA h g −1 , and the Coulombic efficiency remained more than 97% after 20 cycles. All results share the evidence that this research achieved the appropriate amount of TiO 2 , which significantly enhanced the electrolyte properties of CP-SPE.