Electrospun TiO2 nanofibers were synthesized by optimizing various electrospinning conditions. The effect of the precursor's concentration present in sol used for electrospinning was studied for the performance of hybrid photovoltaic devices. The synthesized nanofibers were characterized by XRD and UV-Vis absorption spectroscopy and morphology of the fibers were investigated by FE-SEM. The surface of fibers was modified, and these modified fibers were applied to P3HT/TiO2/N719 composite nanofibers photovoltaic devices. The device performance was investigated by analysis of the incident photon to current conversion efficiency and a J-V characteristic under 1.5G illuminations, which show that efficiency of the devices, can be improved from 0.13% to 0.83% by introducing TiO2 nanofibers synthesized by optimum precursor's concentration.