Various TiO2 building blocks i.e., spheres (S-TiO2), rods (R-TiO2), grains (G-TiO2) were produced by electrospinning technique and sensitized by CdS via successive ionic layer adsorption and reaction (SILAR) to investigate their morphological effect on the photovoltaic properties of quantum dot-sensitized solar cells (QDSCs). It was found that QDSCs with G-TiO2 achieved the highest overall conversion efficiency of 1.74% under one-sun AM1.5G illumination, which corresponds to an increase of similar to 100% (0.87%) compared with S-TiO2 and 35% (1.29%) with R-TiO2, respectively. Electrochemical impedance spectroscopy shows a largest recombination resistance for G-TiO2 cells amongst the three which accounts for its superior photovoltaic performance.