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Titania (TiO2) nanoparticles were surface-modified via atom transfer radical polymerization (ATRP) with hydrophilic poly(oxyethylene) methacrylate (POEM), which can coordinate to the TiO2 precursor, titanium(IV) isopropoxide (TTIP). Following application of a sol–gel process and calcination at 450 °C, TiO2 nanospheres with hierarchical pores were generated, as confirmed by the shifting of conduction bands in TiO2 using UV-visible spectroscopy and X-ray photoelectron spectroscopy (XPS). The particle size and morphology of TiO2 were characterized using wide angle X-ray scattering (WAXS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Brunauer–Emmett–Teller (BET) analysis revealed bimodal distribution of TiO2 pore sizes with peaks at 6 nm and 50 nm to afford better penetration of polymer electrolyte, as confirmed by electrochemical …