Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.