Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers were prepared by the electrospinning method and used as polymer electrolytes in dye-sensitized solar cells (DSSCs). The electrolyte uptake and ionic conductivity of electrospun PVDF-HFP nanofibers with different diameters changed significantly, regardless of the nanofiber thickness. The PVDF-HFP nanofibers prepared from a 15 wt% spinning solution showed high ionic conductivity (1.295 S/cm) and electrolyte uptake (947 %). DSSCs based on the 15 wt% PVDF-HFP nanofiber electrolyte showed an electron transit time of 6.34 x 10(-3) s, electronic recombination time of 5.88 x 10(-2) s, and conversion efficiency of 3.13 %. Thus, we concluded that the electrospun PVDF-HFP nanofibers can be used as polymer electrolytes in flexible DSSCs as well.