Since the gel polymer electrolytes based on polyacrylonitrile (PAN) host have not been sufficient to fulfil the requirements as a separator of current lithium polymer battery, a new polymer host copolymerized with PAN, polyacrylonitrile-co-bis[2-(2-methoxyethoxy)ethyl]itaconate (abbreviated as PANI), was synthesized in expectation of enhanced trapping ability of liquid electrolytes. Electrical, electrochemical, thermal and mechanical studies have been carried out on PAN and PANI blended gel polymer electrolytes, complexed with ethylene carbonate (EC) and γ-butyrolactone (BL) containing LiClO4 salt. The addition of PANI as a host polymer in the PAN-based gel polymer electrolytes has beneficial effects such as higher ionic conductivity, better thermal and electrochemical stabilities and enhanced ability of trapping organic solvent, possibly due to ion chelating ability of itaconate unit, though it shows less mechanical rigidity caused by amorphization of the PAN matrix.