Chromium-, manganese- and cobalt-doped titanium dioxide photocatalysts containing 0.2, 0.5 or 1 at.% of metal-dopant were investigated by UV-VIS, FT-IR, near-IR and electron paramagnetic resonance (EPR) spectroscopic techniques. The presence of the doping ions in the titania structure caused significant absorption shift to the visible region compared to pure TiO2 powder (P25 Degussa). The EPR spectra of TiO2 powders containing chromium showed the superposition of three types of individual paramagnetic species (beta-, gamma- and delta-signals), whose relative EPR intensity is significantly dependent on the dopant concentration, as well as on the photocatalysts preparation and treatment. The EPR spectra of the chromium-doped photocatalysts heated in H-2/N-2 atmosphere corresponded to the Cr(III) ions occupying vacated cation sites in the rutile or anatase crystal lattice. The characteristic feature of the EPR spectra of the Mn/TiO2 samples is a sharp six-line Mn(II) component centered on g(eff) = 1.99, flanked by shoulders with a weak feature, which appeared on g(eff) = 2,66 and 4.32. The photocatalytic activity of the various metal-doped TiO2 samples was tested in aqueous or dimethylsulfoxide (DMSO) suspensions using EPR spin trapping technique with 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trap. The ability of the irradiated photocatalysts to generate reactive oxygen species, namely hydroxyl radicals and super-oxide anion radicals, which were trapped as the corresponding (DMPO)-D-.-adducts was investigated.