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The exploration of polymer electrolyte in the field of dye sensitized solar cell (DSSC) can contribute to increase the invention of renewable energy applications. In the present work, the influence of imidazole on the poly (vinylidene fluoride) (PVDF)–poly (methyl methacrylate) (PMMA)–Ethylene carbonate (EC)–KI–I2polymer blend electrolytes has been evaluated. The different weight percentages of imidazole added into polymer blend electrolytes have been prepared by solution casting. The prepared films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), UV–visible spectra, photoluminescence spectra and impedance spectroscopy. The surface roughness texture of the film was analyzed by atomic force microscopy (AFM). The ionic conductivity of the optimized polymer blend electrolyte was determined by impedance measurement, which is 1.95 × 10−3 S·cm−1at room temperature. The polymer electrolyte containing 40 wt% of imidazole content exhibits the highest photo-conversion efficiency of 3.04% under the illumination of 100 mW·cm−2. Moreover, a considerable enhancement in the stability of the DSSC device was demonstrated.