Room-temperature ferromagnetism in doped anatase TiO2 has previously been observed, ferromagnetic semiconductor heterostructures based on anatase TiO2 can thus provide a new opportunity to study spin-dependent transport phenomena at room temperature. An accurate determination of barrier heights or band offsets at the TiO2-based heterojunctions is of great importance for the spintronics application with semiconductors. X-ray photoelectron spectroscopy with high-energy resolution was used to determine the band offsets of epitaxial LaAlO3/TiO2 heterojunction on SrTiO3(001) substrate fabricated by pulsed laser deposition. Results showed an upward band bending of 0.48(0.03) eV when the film thickness of the overlayer LaAlO3 above 4 unit cells. The valence band offset obtained is about 0.35(0.16) eV. Assuming bulk band gaps for the LaAlO3 and TiO2 epitaxial films, the associated conduction band offset is about 2.95(0.16) eV. These results show that LaAlO3 can be an ideal tunneling barrier for TiO2-based heterojunctions.