In this work modification of TiO2 thin films structure by doping with europium was described. Nanocrystalline films were prepared by high energy magnetron sputtering process. The influence of europium on the microstructure of TiO2 was determined based on the results of X-ray diffraction, transmission electron microscopy, Raman spectroscopy and photoluminescence measurements. It was found that undoped film had rutile structure directly after deposition (without additional annealing), while 0.2 at.% and 0.4 at.% of the dopant was sufficient to receive TiO2 films with anatase form. The type of structure was confirmed with the aid of Raman spectroscopy and by TEM observations. The amount of Eu-dopant had direct impact on PL intensity as well as presence of defect (voids) in the film.