Polymeric sol–gel route has been used for the preparation of TiO2 and RE2O3–TiO2 (RE = Eu, Er) mesoporous thin films by evaporation induced self-assembly method using Si (100) as a substrate. The influence of the relative humidity (RH) on the preparation of the film has been studied being necessary to work under 40% RH in order to obtain homogeneous and transparent thin films. The films were annealed at different temperatures until 900 °C/1 h and the anatase crystallization and its crystal size evolution were followed by low angle X-ray diffraction. Neither the anatase–rutile transition nor the formation of other compounds was observed in the studied temperature range. Ellipsoporosimetry studies demonstrated that the thickness of the thin films did not change after calcination at 500 °C, the porosity was constant until 700 °C, the pore size increased and the specific surface area decreased with temperature. Moreover, the effect of the doping with Er3 + and Eu3 + was studied and a clear inhibition of the crystal growth and the sintering process was detected (by transmission electron and atomic force microscopy) when the doped films are compared with the undoped ones. Finally, Eu3 + and Er3 + f–f transitions were detected by PL measurements. ; Peer reviewed