The effects of gel polymer with chelating groups on polymer matrix were been characterized by differential scanning calorimeter (DSC) and Fourier transform infrared spectroscopy (FT-IR). The mechanical properties were elucidated using an Instron instrument. The gel polymer, poly(AN-co-GMA-IDA), was made by the copolymerizing acrylonitrile (AN) and (2-methylacrylic acid 3-(bis-carboxymethylamino-2-hydroxy-propyl ester) (GMA-IDA), mixing the product with a plasticizer—propylene carbonate (PC). In a study on gel-type polymer electrolytes, lithium perchloride was doped into the gel polymer. FT-IR and 7Li solid-state NMR spectra elucidate the interactions between lithium ions and the unpaired electrons on the groups based on the gel polymer. Additionally, the 7Li solid-state NMR reveals that lithium ions are preferentially coordinated with the GMA-IDA segments. The glassy transition temperature (T g) of the gel-type polymer electrolyte increases with the doping of LiClO4, indicating interactions among lithium ions, the plasticizer (PC) and the copolymer. The Arrhenius-like behavior of the conductivity reveals that the charge carries move in a liquid-like environment. The maximum conductivity in this investigation is 2.17×10−3 Scm−1. The GMA-IDA unit in the gel-type polymer electrolytes improves the dissociation of the lithium salt and the mechanical strength and conductivity of the electrolytes.