The behaviors of lithium ions in a comb-like polymer electrolyte with chelating functional group complexed with LiCF3SO3, LiBr and LiClO4 were characterized by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, AC impedance, and C-13 solid-state NMR measurement. The comb-like copolymer was synthesized from poly(ethylene glycol) methyl ether methacrylate (PEGMEM) and (2-methylacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester) (GMA-IDA). FT-IR spectra reveal the interactions of Li+ ions with both the ether oxygen of the PEGMEM and the nitrogen atom of the GMA-IDA segments. FT-IR spectra also indicate an increasing anion-cation association consistent with increasing LiCF3SO3 concentrations. Moreover, the C-13 solid-state NMR spectra for the carbons attached to the ether oxygen atoms exhibited significant line broadening and a slight upfield chemical shift when the dopant was added to the polymer. These findings indicate coordination between the Li cation and the ether oxygens in the PEG segment. T-g and T-d of copolymers doped with salts clearly. increase, as shown by DSC and TGA measurements. These results indicate the interactions of Li+ with both PEGMEM and GMA-IDA segments form transient cross-links inside the copolymers. The Vogel-Tamman-Fulcher (VTF)-like behavior of conductivity implies the coupling of the charge carriers with the segmental motion of the polymer chain in this study. The maximum conductivity of copolymers relates to the composition of the copolymers and the concentration of doping lithium ions. In summary, the GMA-IDA unit in the copolymer promotes the dissociation of the lithium salt, the mechanical strength and the conductivity of the polyelectrolyte.