The e-beam irradiation technique was found to be a new efficient method to improve and control the morphological and electrochemical properties of composite electrolytes of polyethylene oxide (PEO) and TiO2 for dye-sensitized solar cell (DSSC). PEO was irradiated by electron beam (e-beam) with energy source 2 MeV from 60 to 240 kGy doses at the dose rate of 15 kGy/min. The transition and amorphous phases of PEO were significantly increased upon the e-beam irradiation. Optimum e-beam irradiation was 60kGy in terms of degree of cross linking and amorphicity for the efficient ion conduction electrolytes. However, the properties of polymer and composite electrolytes were deteriorated after irradiation of > 60 kGy. The prepared composites with PEO/60kGy and TiO2 (PEO/60kGy-TiO2) showed significantly improved morphological and ionic conductivity properties of electrolyte for DSSC. DSSC fabricated with PEO/60kGy-TiO2 showed drastically increased conversion efficiency of 4.52% as compared to DSSC fabricated with bare PEO (conversion efficiency = 1.9%).