We report a new phenomenon that may possibly enable the selective detection of solvent/surface interactions on a buried TiO2 surface. A mechanism based on intermolecular Fano resonance involving a solvent vibrational mode and a TiO2 phonon mode is proposed, which suggests that the strong electronic character of the TiO2 phonon mode plays an important role. The solvent vibrational mode that takes part in Fano resonance can be significantly enhanced with the help of the intense resonance hyper-Raman band of a TiO2 phonon mode, and this allows us to selectively detect the solvent/surface interactions even from a buried surface.