Titanium dioxide is a promising candidate for photocatalytic H2 fuel production, and understanding water splitting on TiO2 surfaces is vital toward explaining and improving the generation of H2. In this work, we electron irradiate anatase TiO2(101) at room temperature to create metastable surface oxygen vacancies in order to investigate their ability to dissociate H2O. Our scanning tunneling microscopy investigations suggest that the surface oxygen vacancies can dissociate H2O by forming bridging OH species. This claim is supported by theoretical calculations from the literature and our previously published spectroscopic measurements.