A new copolymer polyacrylonitrile-co-bis[2-(2-methoxyethoxy)ethyl]itaconate (abbreviated as PANI) was synthesized in the hope of getting a polymer host having a better ability of trapping organic solvent to overcome the drawbacks of polyacrylonitrile (PAN) system gel polymer electrolytes. Blend of PAN and PANI was complexed with organic solvents, ethylene carbonate (EC) and γ-butyrolactone (BL), and LiClO4 salt. The highest room temperature conductivity of 1.9×10−3 Scm−1 was found for a film of 25PAN–10PANI–50EC/BL–15LiClO4. The PANI was found to effectively trap organic solvents and, therefore, greatly enhance the miscibility of polymer host and solvents, possibly due to ion chelating ability of itaconate unit. The PAN–PANI blend gel-electrolyte, as compared with pristine PAN-based electrolyte, had better electrochemical stability and was more stable toward lithium electrode, though it exhibited slightly less mechanical rigidity caused by amorphization of the PAN matrix.