Different weight percentages (1, 3 and 5 wt%) of the Al2O3 nanoparticles (NPs) embedded TiO2 nanofibers (NFs) were prepared by the electrospinning technique. A mixture of titanium isopropoxide, acetic acid, Al2O3 NPs and PVP in ethanol were used. X-ray diffraction studies confirmed the formation of anatase and mixed phase (anatase/rutile) for the pure TiO2 NFs and Al2O3 NPs embedded TiO2 NFs, respectively. SEM and TEM studies showed the morphologies of Al2O3 NPs embedded TiO2 NFs and their average diameter was found to be similar to 83 nm. The chemical composition of TiO2 NFs was confirmed by EDX analysis. The effects of Al2O3 NPs embedded TiO2 nanofibers on the adsorption of dye and the charge transfer resistances were studied using UV-vis spectroscopy and electrochemical AC-impedance studies. Dye sensitized solar cells were fabricated using different weight percentages of Al2O3 NPs embedded TiO2 NFs as photoanodes and Pt as counter electrode and 0.5 M 1-butyl-3-methylimidazolium iodide, 0.5 M LiI, 0.05 M I-2, 0.5 M 4-tertbutylpyridine in acetonitrile as the electrolyte. Among the three photoanodes tried, the cell fabricated using 3 wt% of Al2O3 NPs embedded TiO2 NFs as photoanode had an improved photocurrent efficiency (PCE) of 36.2% compared to other similar systems in the literature. This might be due to an improvement in dye adsorption by the addition of a basic oxide (Al2O3) and also the formation of a rutile phase (15.7%), thereby retarding the charge recombinations inside the DSSC and in turn increasing the V-oc and the J(sc) of the cell.