Use of Ceramic filler is one of the most common approaches to improve the conductivity and stability properties of a solid polymer electrolyte (SPE) cum separator. Among them, active fillers like Garnet have been extensively used to enhance the stability and conductivity of SPE. However, SPE suffers from limited ion migration at room temperature acting as a bottleneck for their application in all solid-state batteries. An extensive study on these fillers' role in ion dissociation and migration can be a stepping stone for advanced SPE. In the present work, an FTIR analysis has primarily been used to identify and evaluate cation coordinate site-cation, and ion pair interactions in a Li6.5La3Zr1.75Te0.25O12 loaded polyethylene oxide-LiCF3SO3 matrix with varying ceramic concentrations. Further, the Trukhan model has been used to calculate diffusion coefficient, mobility, and charge carrier density to interpret relaxation parameters, conductivity, and FTIR results in the SPE samples. Finally, an ion migration model has been proposed based on the results obtained in experimental studies.