Dye-sensitized solar cells (DSSCs) were fabricated using electrospun titanium dioxide (TiO2) nanofibers as photoelectrodes. The electrospun TiO2 nanofibers photoelectrodes possess unique structural features that offer high surface area for enhanced dye loading and enable the fast and effective transport of electrons to the collection electrode. Using the electrospinning technique, the nanofibers were grown directly onto the fluorine-doped tin oxide glass from a typical spinning of solution. The solution is that the titanium isopropoxide and polyvinyl acetate are composited in N,N-dimethylformamide. The characteristics of electrospun TiO2 nanofibers were investigated by scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and X-ray diffraction. DSSC characteristics were investigated by current density-voltage curve, open circuit voltage decay (OCVD), and electrochemical impedance spectroscopy (EIS) measurements. OCVD and EIS analyses revealed that cells based on TiO2 nanofiber photoelectrodes possess lower transfer resistance and longer electron lifetime than nanoparticle based cells.