Ionic mobility of electrolyte materials is essentially determined by the nanoscale interactions, the ion-ion interactions and ion-solvent interactions. We quantitatively evaluated the interactive situation of the lithium polymer gel electrolytes through the measurements of ionic conductivity and diffusion coefficients of the mobile species of the lithium polymer electrolytes. The interactive force between the cation and anion in the gel depended on the mixing ratio of the binary solvent, ethylene carbonate plus dimethyl carbonate (EC/DMC). The gel with the solvent (3:7 EC:DMC) showed minimal cation-anion interaction, which is the Caine. of the highest ionic mobility compared with those of the other gels with different solvents This suggests that the cation-anion interaction does not simply depend On the dielectric constant of the solvent but is associated with the solvation condition of the lithium. In the Case of the gel with the 3:7 EC/DMC solvent, most of the EC species strongly coordinate to a lithium ion, forming the stable solvated lithium; Li(EC)(3)(+), and there are no residual EC species for exchange with them. As a result, the solvating EC species would be a barrier that restricts the anion attack to the lithium leading to the smallest cation-anion interaction. On the other hand, interaction between the cation and polar sites, hydroxyl and oxygen groups of ether of the polyvinyl butyral (PVB) and polyethylene oxide (PEO) polymer, respectively, in the gels was another dominant factor responsible for cation mobility. It increased with increasing polar site concentration per lithium. In case of the PVB gels, cation anion interaction increased with an increasing polymer fraction of the gel contrary to the independent feature of PEO gels with the change of the polymer fraction. This indicates that the cation-anion interaction is associated with the polymer structure of the gel characterized by the kind and configuration of polar groups, molecular weight, and network morphology of the polymer.