Titanium dioxide (TiO2) is an excellent photoanode material in dye-sensitized solar cells (DSSCs). However, the surface morphology of TiO2 nanoparticle has some disadvantages such as weak dye adsorption capacity and low electron mobility leading to low performance of DSSCs. In this study, TiO2 nanofibers (NFs) were prepared by electrospinning technology and doped with reduced grapheme oxide (rGO) and zirconium dioxide (ZrO2) to modify the photoanode of DSSCs. For exploring its properties and the impact of photovoltaic performance, NF can not only improve the particle arrangement but also increase its specific surface area to facilitate the adsorption of dye in DSSCs. rGO is characterized by good electrochemical property and excellent electron conduction. The doped ZrO2 improves the photovoltaic performance of the DSSCs in order to reduce charge recombination. The composite NF is employed to increase the surface area to promote the adsorption of dyes in DSSCs and improve the power conversion efficiency. The power conversion efficiency (eta) of the DSSCs with modified photoelectrode by ZrO2 and rGO doped TiO2 composite NF is 5.44% and eta increases 75% compared with the DSSCs without modified photoelectrode.