In the catalytic field, the Au/TiO2 interface plays an important role due to an extraordinary high activity. We investigated the electronic state of the Au/TiO2 (320) interface by second harmonic generation (SHG) technique. The Au thin film was fabricated on a stepped TiO2 (320) substrate with thickness of 2 nm in a UHV chamber at a pressure of 2x10-7 Torr. We observed the azimuthal angle and polarization dependent SHG intensity from Au/TiO2 (320) interface and bare TiO2 (320) using both 1064 nm and 532 nm wavelength of pulsed Nd:YAG laser light as fundamental sources. When using 1064 nm, we found isotropic response from both the samples. The anisotropic behaviour was observed from both the samples when using 532 nm wavelength of laser light. This anisotropic response was observed due to the electronic resonance from Au/TiO2 interface in the UV region that may be related to many catalytic reactions.