Pure TiO2 and copper-doped TiO2 (Cu-TiO2) films were prepared on LaAlO3(111) substrates by molecular beam epitaxy. We found that the Cu-TiO2 films could enhance the Raman scattering of LaAlO3. The Raman scattering of the LaAlO3 substrates is selectively enhanced in the Cu-doped TiO2/LaAlO3 heterojunctions. The doped Cu on TiO2 can enrich the energy level states of TiO2, which is attributed to the dominant contribution of the TiO2-to-LaAlO3 charge transfer (CT) mechanism. This work is valuable in developing doped TiO2 films which are promising materials used in the field of surface-enhanced Raman scattering as well as in studying the CT mechanism between Cu and TiO2 for potential photoelectrochemical applications. (C) 2015 Elsevier B.V. All rights reserved.