Polymer electrolyte films, comprising ammonium trifluoromethanesulfonate salt and butyl-trimethyl ammonium bis(trifluoromethylsulfonyl)imide ionic liquid immobilized in poly (ethyl methacrylate) was studied. Structural, morphological, thermal and electrical properties of the polymer electrolyte films were investigated by differential scanning calorimetry, scanning electron microscopy, and impedance spectroscopy, respectively. Interactions of the salt and ionic liquid with the host polymer were investigated by Fourier transform infra-red spectroscopy. Electrochemical stability of the electrolytes was determined using linear sweep voltammetry and transference numbers corresponding to ionic transport has been evaluated by means of the Wagner polarization technique. The highest conductivity achieved is in the order of 10−4 S cm−1 for the film added with 35 wt % butyl trimethylammonium bis (trifluoromethanesulfonyl)imide. The film has high amorphicity and low glass transition temperature of 2 °C. The film is electrochemically stable up to 1.8 V. The ion transference number in the polymer film is 0.82 and the conductivity behavior obeys Vogel-Tamman-Fulcher equation.