Titanium dioxide (TiO 2) photoelectrode is one of the most important components in a dye-sentisized solar cell (DSSC). In common, the overall performance of the DSSC depends on the surface area of the TiO 2 photoelectrode which is directly correlated to the amount of dye loading. Dye loading increased with the increase in the surface area of TiO 2 layer that enhanced short circuit current (J sc) performance in DSSC. In addition, for better penetration of electrolytes, it is essential to use the mesoporous or macroporous TiO 2 photoelectrode structure than microporous TiO 2 photoelectrode structure. The photoelectrode made up of from commercially available TiO 2 (P25, Degussa) has limitations mainly because of lower surface area which motivated us to modify it by atom transfer radical polymerization (ATRP) process with hydrophilic poly(ethylene glycol) methyl ether methacrylate (POEM). Dye-sensitized solar cells (DSSCs) made from TiO 2 spheres with hierarchical pores exhibited improved photovoltaic efficiency (3.30% for low molecular weight (M w) and 2.50% for high M w polymer electrolytes), as compared to those from pristine TiO 2 nanoparticles (2.40% for low M w and 1.30 % for high M w) at 100 mW/cm 2, due to the increased surface areas and light scattering.