Thin films of poly acrylonitrile (PAN) doped with sodium Fluoride (NaF) were prepared by solution casting technique. The Gel polymer Electrolyte films have an average thickness of 142 µm.The films were prepared with different (wt%) ratios. The structural formations were analyzed by X-Ray Diffraction method (XRD).The alternating current (AC) Conductivity and thermal conductivity of the gel polymer electrolyte composites were studied as function of applied frequency, temperature and NaFconcentration. The AC conductivity was determined fromthe impedance data and thermal conductivity was measured using the transient electric pulse method. It was found that the AC Conductivity increases with increasing temperature and NaF Concentration.The formed fluoride complexes also contribute in increasing the AC quantities. It was also found that the thermal conductivity of the gel polymer electrolyte films increases with both temperature and NaF concentration.The DSC measurements showed a decrease in the degree of crystallinity and increase of amorphous regions with increasing concentration of saltNaF. The sample containing 30 wt% of NaF exhibited the highest conductivity of 1.82x10-4 S cm-1at room temperature (303K) and 2.96x10-3 S cm-1 at 373K.