Polymer electrolytes containing ionic liquid (IL), 2-methyl-1,3-dipropylimidazolium dihydrogenphosphate (MDPImH(2)PO(4)) have been studied by H-1 solid state NMR and differential thermal analysis (DTA) simultaneously by using a specially designed probe. To the best of our knowledge, this is the first report of its kind for IL based polymer electrolytes. The variation of NMR line width with temperature for the IL and polymer electrolytes shows line narrowing at the glass transition and melting temperature. The onset of long-range ion diffusional motion also takes place at these temperatures and is accompanied by a sudden increase in ionic conductivity value by 2-3 orders of magnitude. The presence of amorphous and crystalline phases in IL based polymer electrolytes has been observed from X-ray diffraction (XRD) studies, and the amorphous phase is the high conducting phase in these polymer electrolytes. The IL-based polymer electrolytes have been observed to be thermally stable up to 200 degrees C. The results obtained from ion transport studies been supported by Fourier transform infrared (FTIR), XRD, and cyclic voltammetry (CV) studies.