This work introduces the synthesis of N-doped nanocomposite of ZrO2/TiO2 nanofibers (NFs) by use of both electrospinning and hydrothermal methods. The physicochemical properties of the introduced TiO2 NFs are investigated to describe the morphology, crystallinity and chemistry through FESEM, SEM-EDX, XRD, TEM and XPS. As the results, the investigated material can be described as N@ZrO2/TiO2 NFs. The crystal structure of the prepared TiO2 is only anatase structure. Then, the novel NFs are utilized to design novel photoanode and photo-electrochemical characterization such as current-potential response under light, incident photon-to-current efficiency (IPCE) and electrochemical impedance spectroscopy (EIS) of the dye-sensitized solar cell (DSC) are also investigated. The photovoltaic response showed that the efficiency of the DSCs employed N@ZrO2/TiO2 photoanode gave 4.95%, which was higher than those of DSCs designed with ZrO2/TiO2 NFs (4.51%) and N@TiO2 NFs (4.41%) photoanodes. The high photo-response of DSC by use of N@ZrO2/TiO2 NFs can be attributed to enhanced electrical conductivity, which is studied via EIS, and presence of active sites of N. These active sites can easily absorb dye-molecules in the step of dye-loading in the fabrication of DSC. (C) 2016 Published by Elsevier Inc.