Solid polymer electrolytes (SPEs) have gained interest due to their possible use as solid state alternatives of liquid electrolytes in various electrochemical devices like batteries and photovoltaic devices. Use of organic solvent-based volatile liquid electrolyte in these devices, leads to the decay in the cell performance due to the evaporation and leakage. Replacing liquid electrolytes by SPEs is one of the best remedies of these problems. Among various SPEs, PEO based electrolytes have drawn more attraction due to their high thermal stability and stable ionic conductivity. Due to these properties, the use of PEO based SPEs in dye-sensitized solar cells (DSCs) has come up as promising alternative. In this work, we explore the potential of the PEO/Polydimethylsiloxane(PDMS) blend polymer electrolyte in DSCs compared to only PEO electrolyte. We have prepared Li+ conducting SPEs with different PEO/ PDMS ratio. The structural characterizations of SPEs were carried out by DSC, FT-IR, OM, and SEM. The ion conducting properties of the polymer films have been found to show many fold jump when compared to the pure PEO electrolyte. The electrolyte dissociation theory has been employed to explain the conductivity behavior. The blend electrolyte containing the I-/ I3- couple were used for fabricating the solid-state DSCs. The photovoltaic performance of DSC with PEO/PDMS blend electrolyte is reported in detail in this paper and found to have enhanced fill factor and conversion efficiency compared to PEO electrolyte. It has been established that the introduction of PDMS decrease the crystallinity of the blend electrolytes. As a result, this blend electrolyte has improved ionic conductivity and show better conversion efficiency.