The electrical characteristics of Au/n‐TiO2Schottky diodes have been studied usingI‐VandC‐Vmeasurements. TiO2samples with working face perpendicular to thecaxis are reduced in a vacuum of 10−6Torr at 800 °C for about 5 h and then quenched. The resistivities are in the range 20–30 &OHgr; cm. The barrier heights deduced fromI‐Vcharacteristics in agreement with the thermionic emission theory are in the range 0.87–0.94 eV.C‐Vdata yield lower barrier heights and show a frequency dependence attributed to relaxation phenomena occurring in a disturbed layer near the surface. Comparison with results relative to Au/n‐SrTiO3diodes shows that the barrier heights obey the Schottky model for these ionic semiconductors, confirming the role of the electron affinity in the band bending formation.