The work functions of nanocrystalline anatase ( TiO ₂) thin films and a rutile single crystal were measured using photoemission spectroscopy (PES). The nanocrystalline titanium dioxide films were deposited in-vacuum using electrospray thin film deposition. A comparison between ultraviolet photoemission spectroscopy (UPS) and low intensity x-ray photoemission spectroscopy (LIXPS) work function measurements on these samples revealed a strong, immediate, and permanent work function reduction (>0.5 eV ) caused by the UPS measurements. Furthermore, it was found that regular XPS measurements also reduce the work function after exposure times ranging from seconds to minutes. These effects are similar in magnitude to artifacts seen previously on indium tin oxide (ITO) substrates characterized with XPS and UPS, and are likely related to the formation of a surface dipole through the photochemical hydroxylation of oxygen vacancies present on the TiO ₂ surface.