The preparation of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmImTFSI)-based poly(methyl methacrylate)-poly(vinyl chloride), PMMA-PVC, gel polymer electrolytes was done by solution casting technique. The ionic conductivity of gel polymer electrolytes was increased, up to a maximum value of (1.64 +/- 0.01) x 10(-4) S/cm by adding 60 wt% of BmImTFSI. Conductivity-frequency dependence, dielectric relaxation, and dielectric moduli formalism were also further analyzed. These studies assert the ionic transportation mechanisms in the polymer matrix. Occurrence of polarization electrode-electrolyte interface is also observed. This leads to the formation of electrical double layer and hence indicates the non-Debye characteristic of the polymer matrix in the dielectric studies. Based on the changes in shift, changes in intensity, changes in shape, and existence of new peaks, attenuated total reflectance-Fourier transform infrared divulged the complexation between PMMA, PVC, lithium bis(trifluoromethanesulfonyl)imide, and BmImTFSI, as shown in the infrared spectra.