The adsorption of 3-(triethoxysilyl)propionitrile (TESP) on a reduced rutile TiO2(110) surface has been investigated using synchrotron-based X-ray photoelectron spectroscopy in ultrahigh vacuum (UHV). We have studied TESP adsorption on two surface preparation of rutile TiO2 (110) to explore the role of surface defects. In the first preparation, the adsorption of TESP was studied on reduced TiO2 (110) surface at room temperature. In the second experiment TESP was adsorbed on the oxygen-treated TiO2 surface to quench the oxygen vacancies generated by UHVannealing of the TiO2 crystal. The molecular footprints of the TESP molecules confirms the adsorption on both types of TiO2(110) surfaces. In the case of the reduced surface, temperature-dependent XPS measurements show the thermal stability of TESP molecules up to 600 °C. The comparison of the nitrogen and carbon lineshapes for both preparations suggests different adsorption geometries on the reduced and oxygen-dosed surfaces. To the best of our knowledge, the UHV preparations and measurements of TESP adsorption on rutile TiO2 (110) in the present study are reported for the first time.