In this work analysis of the structural and optical properties of TiO2 thin films doped with terbium has been described. Samples were prepared by a high energy reactive magnetron sputtering process under low pressure of oxygen plasma. X-ray diffraction results have shown that different TiO2 crystal forms have been produced, depending on the amount of Tb dopant. The undoped matrix had rutile structure with crystallites with a size of 8.7 nm, while incorporation of 0.4 at. % of Tb into the film during the sputtering process resulted in anatase structure with bigger crystallites (11.7 nm). Increasing the amount of terbium up to 2 at. % and 2.6 at. % gave rutile structure with crystallites with a size of 6.6 nm for both films. However, Raman spectroscopy has revealed that in the case of TiO2:(2 at. % Tb), except for the rutile form, the presence of fine-crystalline anatase was observed. Moreover, the lack of Raman peaks shift attests to the lack of stress in the titania lattice of all of the TiO2:Tb films. This fact indicates localization of Tb3+ ions on the surface of TiO2 nanocrystals. In the case of optical investigation, results have shown that doping with terbium has a significant influence on the properties of TiO2, but it does not decrease the high transparency of the matrix. The observed changes of the transmission characteristics were produced only due to modification of the TiO2:Tb structure. Photoluminescence measurements have shown that emission of light from TiO2:Tb films occurs when the amount of terbium is 2.6 at. %. Based on the obtained results a scheme of direct energy transfer from titanium dioxide matrix (with rutile structure) to Tb3+ ions has been proposed.