Poly(ethylene carbonate) (PEC) is known as an alternating copolymer derived from carbon dioxide (CO2) and an epoxide as monomers. Here, we describe a new quaternary PEC-based composite electrolyte containing lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, N-n-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (Pyr14TFSI) ionic liquid, and an electrospun silica (SiO2) fiber (SiF) with a submicron diameter in view of its possible applications in solid-state Li polymer batteries. A free-standing electrolyte membrane is prepared by a solvent casting method. The Pyr14TFSI ionic liquid enhances the ionic conductivity of the electrolyte as a result of its plasticizing effect. The electrochemical properties, such as ionic conductivity and Li transference number (t Li+), as well as mechanical strength of the electrolyte, are further improved by the SiF. We show that the quaternary electrolyte has a conductivity of the order of 10−7 Scm−1 at ambient temperature and a high t Li+ value of 0.36 with an excellent flexibility. A prototype Li polymer cell using LiFePO4 as a cathode material is assembled and tested. We demonstrate that this battery delivers a reversible charge-discharge capacity close to 100mAh g−1 at 75°C and C/15 rate. We believe that this work may pave the road to utilize CO2 as a carbon source for highly-demanded, functional battery materials in future.