Low-frequency surface vibrations were observed on a rutile TiO2(110) surface covered with trimethyl acetate (TMA) by using fourth-order Raman spectroscopy. The TMA-covered surface interfaced to air was irradiated with 18-fs light at a wavelength of 630 nm. A pump pulse excited vibrational coherence of Raman-active modes and a probe pulse interacts with the coherently excited surface to generate second harmonic light (315 nm), the intensity of which oscillated as a function of the pump-probe delay. Four bands were recognized at 180, 357, 444, and 826 cm(-1) in the Fourier transformation spectrum of the oscillation and assigned to bulk phonons modified by the presence of the surface boundary condition. The Raman transition for the pump was nonresonant to the band gap excitation of TiO2, as evidenced by the oscillation phase relative to the pump irradiation and by the oscillation amplitude as a function of the pump power. The observable range of this surface-selective spectroscopy is extended to wide-band gap materials on which one-photon resonance enhancement of the Raman-pump efficiency cannot be expected.