One dimensional nanostructures with diameter comparable to wavelength of visible light and optimized anatase/rutile phase can effectively provide improved light scattering and high charge transport network. In this direction, TiO2 nanofibers (NFs), with variable diameters (120–450 nm), have been prepared using electrospinning technique. As a case study, Dye sensitized solar cells (DSSCs) have been fabricated by incorporating TiO2 NFs in the photoanode with TiO2 nanoparticles (NPs) and have been found to exhibit enhanced PCE as compared to TiO2 NPs based DSSC. The enhanced PCE of TiO2 NFs based DSSC is due to combined effect of efficient light scattering augmented from Mie scattering theory and faster electron transport confirmed through electrochemical impedance spectroscopy. TiO2 NFs with mean diameter of 230 nm based DSSC have been found to exhibit optimal performance and PCE of 7.45% compared to TiO2 NPs based DSSC (5.27%). Moreover, the PCE increases to 7.98% on optimizing TiO2 NFs’ wt% in the photoanode.