This study elucidates the size effect on dye-sensitized solar cells (DSSCs) by synthesizing highly uniform hierarchical hollow sphere TiO2 samples, with the diameters from 220 nm to 800 nm. Experimental results indicate that the optimum conversion efficiency using N719 dye can be achieved around 5.5%, as the diameter of hierarchical hollow spheres is 450-550 nm. According to the incident photon-to-current conversion efficiency (IPCE) spectra, large-sized hierarchical hollow spheres significantly enhance the light harvesting by scattering; whereas small-sized hallow spheres (<360 nm) improve negligibly. Additionally, mesoporous and solid spheres with an identical diameter, 440 nm in this study, are also studied as a comparison. Our results demonstrate that hollow spheres perform the same conversion efficiency as that of mesoporous spheres owing to the equivalent adsorption of dye molecules in both hierarchical structures - regardless of the surface area of the interior of mesoporous structure, which shows that hollow spheres have higher conversion efficiency per unit volume than that of mesoporous spheres. (C) 2014 Elsevier B.V. All rights reserved.