The new phase, where peroxo groups are incorporated into titania particles, along with anatase and hydrated η-TiO 2 with peroxo groups on the surface of titania nanoparticles, were prepared by introduction of H 2 O 2 into reaction mixtures while synthesizing TiO 2 from TiOSO 4 or by cold impregnation of pre-synthesized TiO 2 . The samples were studied by a complex of methods (classical and synchrotron-radiation X-ray powder diffraction, small-angle X-ray scattering, high-resolution scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray absorption spectroscopy, IR and Raman spectroscopy, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance and absorption spectroscopy, DSC). The [TiO x (O 2 ) 2-x (H 2 O) m ] phase was first structurally characterized and compared to η-TiO 2 . Most samples of H 2 O 2 -sensitized TiO 2 discolor methyl orange under visible light irradiation faster than commercial Hombikat UV100 treated with H 2 O 2 . The activity of the samples strongly relating to their phase composition was associated with existence of large amount of titanium peroxo complexes along with formation of mixed-phase samples.