Transition metal oxide surfaces and interfaces are exploited for a broad range of applications including heterogeneous catalysis, chemical sensing, and microelectronics. Detailed surface science studies of industrially relevant materials and reactions have been hampered by the limited availability of suitable single crystal samples. We have been using epitaxial growth techniques to create high quality films that can then be characterized using surface science techniques such as STM, ISS, UPS and XPS, and TPD. This work focused on W, V, and Ti oxides. We have revealed that transition metal oxides can respond to reduction in different ways. Initial reduction simply removes terminal oxygen atoms from the surface. At higher temperatures, continued reduction causes W5+ migration into the bulk creating pits that eventually organize into regular arrays of rows and troughs. For the row and trough structures, 1-propanol adsorbed solely on the tops of the rows. Molecules adsorbed at these sites followed the same reaction pathway as a fully oxidized surface but at much lower temperatures. To investigate how oxide–oxide interactions influence reactivity, we have been studying the interaction of vanadia layers with WO3 and TiO2. It was found that epitaxial VO2 could be grown ad infinitum on anatase (001). At high growth temperatures a c(2x2) structure was observed on the surface of these epitaxial VO2 films. Our work on manipulating oxide surfaces has focused on exploiting the ferroelectric effect to reversibly switch the surface structure and thus reactivity of LiNbO3 (0001).