Polymer electrolytes based on the blends of poly(methyl acrylate) (PMA) and poly(vinyl acetate) (PVAc) were prepared using tetrapropylammonium iodide (TPAI) salt and 1-butyl-3-methylimidazolium iodide (BMII) ionic liquid. Single transition between the glass transition temperatures of the constituents indicates the miscibility of PMA and PVAc over the entire composition range. The presence of TPAI and BMII does not affect the miscibility of PMA and PVAc. The complexation in the PMA/PVAc-TPAI-BMII is supported by the differential scanning calorimetry and Fourier transform infrared spectroscopic studies. Conductivity increases by two order of magnitudes with the incorporation of 5 wt% of BMII. Conductivity increment is due to the extra charge carriers provided by BMII. Electrolyte films were sandwiched between titanium dioxide photoanode and platinum counter electrode for dye-sensitized solar cells (DSSCs) assembly. The addition of BMII increases the efficiency of DSSC from 2.79% to 4.62%.