The dye-sensitized solar cell (DSSC) devices using polymer electrolytes based on electrospun poly(vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) nanofibers were fabricated and investigated the photovoltaic performances. The electrospun PVDF-HFP nanofibers were prepared by various parameters such as; polymer concentrations, applied voltages, and tip to collector distances (TCD) by the electrospinning method. The open circuit voltage (V(OC)), short circuit current (J(SC)), fill factor (FF), and overall power conversion efficiency (eta) of DSSC devices using electro-spun PVDF-HFP nanofibers were 0.7180-0.7420 V, 9.7200-10.8837 mA/cm2, 0.5610-0.6250, and 4.1700-5.0186%, respectively. When 15 wt% of polymer concentration, 14 kV of applied voltage, and 14 cm of TCD is applied to fabricate the PVDF-HFP nanofiber, the electrospun PVDF-HFP nanofiber should be the regular diameter of a nanofiber, the power conversion efficiency of the DSSC device reached 5.0186% as the best result.