Mesoporous titania films are prepared via the polymer-template assisted sol-gel synthesis at low temperatures, using the titania precursor ethylene glycol-modified titanate (EGMT) and the diblock copolymer polystyrene-block-polyethyleneoxide (PS-b-PEO). UV-irradiation is chosen as a low temperature technique to remove the polymer template and thereby to obtain titania sponge-like nanostructures at processing temperatures below 100 °C. After different UV irradiation times, ranging for 0 h to 24 h, the surface and inner morphologies of the titania films are studied with scanning electron microscopy (SEM) and grazing incidence small-angle x-ray scattering (GISAXS), respectively. The evolution of the band gap energies is investigated using ultraviolet/visible (UV/Vis) spectroscopy. The findings reveal that 12 h UV-treatment is sufficient to remove the polymer template from the titania/PS-b-PEO composite films with a thickness of 80 nm, and the determined bad gap energies indicate an incomplete crystallization of the titania nanostructures.