Polymer blend electrolyte membrane was prepared for dye sensitized solar cells based on poly ethylene oxide and polyvinylidene fluoride-co-hexaflouropropylene (PVDF-HFP) filled with surface modified Titanium dioxide (M-TiO 2 ) nanofillers. The surface of TiO 2 was modified using Aminopropyltrimethoxysilane. The electrochemical studies indicated that the addition of surface modified nanoparticles increase the ionic conductivity up to 7.21x 10 -4 S/cm for 7 wt%, whereas the ionic conductivity about 8.14×10 -5 S/cm with the addition of unmodified counterpart as the filler into the PEO/PVDF-HFP blend system. In addition to this ionic mobility, charge carrier concentration, ion diffusion coefficient also found to increase with the addition of surface modified TiO 2 nanoparticles. Wide angle X-ray diffraction (WAXD) results showed the change in the crystalline phase of PEO/PVDF-HFP blend electrolyte with the addition of M-TiO 2 . The influence of the TiO 2 nanoparticles surface functionality on the degree of crystallinity of the polymer matrix was analyzed using differential scanning Calorimetry (DSC). Thermo mechanical behavior of the composite membranes was studied by dynamical mechanical Analysis (DMA). The thermo gravimetric investigations (TGA) of membranes indicated the thermal degradation temperatures of hybrid nanocomposites were enhanced upon the addition of nanosized inorganic fillers. The morphological characterizations were carried out by atomic force microscopy (AFM). The solid state dye sensitized solar cell has been fabricated by using silane modified TiO 2 /PEO/PVDF-HFP polymer nanocomposites electrolyte, multiwalled carbon nanotube (MWCNT)/Nafion ® as counter electrode. The photovoltaic characteristics of constructed cells showed an enhancement of open circuit voltage (V oc ) from 0.62 to 0.71 V andthe best efficiency achieved about 2.84%. The enhancement of DSSC was further confirmed by electrochemical impedance spectra (EIS) spectra studies for lowest Warburg resistance (R diff ).