In this thesis, surface sensitive techniques have been employed to investigate the surface chemistry of TiC>2. A bottom-up approach was used to grow ultra-thin films of rutile TiO2(110) on Ni(110). The surface structure of this system was probed using scanning tunnelling microscopy (STM) and low energy electron diffraction (LEED), whereas the electronic structure was characterised with soft X-ray photoelectron spectroscopy (SXPS). SXPS was also used to investigate the reactivity of this system towards water. While optimising the conditions for the growth of the desired titania phase, the growth of other structures commonly found in reduced native TiC>2 crystals were apparent from STM and LEED observations. The formation of 1x2 reconstructed TiO2(110) and crystallographic shear planes are reported. These phases are assigned by comparison with previous studies of analogous phases on the native rutile TiC>2(110) surface. STM was also used to monitor chemical reactions on native TiO2(110) surfaces. The reaction of surface bridging hydroxyl groups with molecular oxygen at room temperature was imaged directly. After exposure to O2, nearly all bridging hydroxyl groups are consumed, and new, mobile adsorbates appear with a range of apparent heights. With the support of calculations performed by Hofer's group in the University of Liverpool and Fisher's group in UCL, the adsorbates left on the surface after the reaction are assigned to neutral and charged oxygen adatoms as well as terminal hydroxyls. Finally, the surface local density of states of TiO2(110) were measured using scanning tunnelling spectroscopy. Energetically localised states are found at sample biases of +0.2 V, 0.7 V and 1.9 V. Additionally, a surface state at 1.9 V is localised spatially at two adjacent titanium five-fold atoms near to the positions of surface oxygen vacancies.