We prepared poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers by the electrospinning method and applied to the polymer matrix in polymer electrolytes for dye-sensitized solar cells (DSSCs). The uptake, ionic conductivity, and porosity of the electrospun PVDF-HFP nanofiber films showed 653 +/- 50%, 4.53 +/- 1.3 x 10(-3) S/cm, and 70 +/- 2.3%, respectively, regardless of the diameter and morphology of nanofibers. In addition, several DSSC devices using the electrospun PVDF-HFP nanofiber films as the polymer matrix were prepared to investigate the photovoltaic effect of iodine (I(2)) concentrations on DSSC devices. With an increase of I(2) concentration in electrolyte solutions, the ionic conductivity increased, while the photocurrent density of DSSC devices decreased. (C) 2008 Elsevier B.V. All rights reserved.