This paper reports the electrospinning fabrication and characterization of TiO2 nanofibers. Various electrospinning process parameters such as applied voltage, distance tip-collector, solution flow rate and polymer (PVP) concentration are studied. The prepared nanofibers were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), thermogravimetric-differential thermal analysis (TG-DTA) and Fourier transform infrared spectroscopy (FTIR). XRD pattern of TiO2 nanofibers evidenced the presence of mixed phases of anatase and rutile. TG/DTA investigation showed the characteristic peaks corresponding to the heating behavior of TiO2-PVP mat. FTIR investigation endorsed a vibration peak at 660 cm(-1) associated with the characteristic Ti-O-Ti bond. With the optimized process parameters, TiO2 nanofibers diameter was found to be reduced to 74 nm as compared to the first sample prepared with the diameter of 343 nm. Furthermore, these nanofibers were employed as the photoanode material for the preparation of dye-sensitized solar cell (DSSC) and photovoltaic study is evaluated.