The Schottky barrier heights at the Pt/TiO2 (001) junctions are modulated over 0.8 eV by inserting <1 nm of LaAlO3. The large electric field in the LaAlO3 is stabilized by preserving the continuity of in-plane lattice symmetry at the oxide interface. These results greatly expand the application of dipole engineering to versatile polycrystalline metal/binary oxide functional interfaces.