The field of photocatalysis can be traced back more than 80 years to early observations of the chalking of titania-based paints and to studies of the darkening of metal oxides in contact with organic compounds in sunlight. During the past 20 years, it has become an extremely well researched field due to practical interest in air and water remediation, self-cleaning surfaces, and self-sterilizing surfaces. During the same period, there has also been a strong effort to use photocatalysis for light-assisted production of hydrogen. The fundamental aspects of photocatalysis on the most studied photocatalyst, titania, are still being actively researched and have recently become quite well understood. The mechanisms by which certain types of organic compounds are decomposed completely to carbon dioxide and water, for example, have been delineated. However, certain aspects, such as the photo-induced wetting phenomenon, remain controversial, with some groups maintaining that the effect is a simple one in which organic contaminants are decomposed, while other groups maintain that there are additional effects in which the intrinsic surface properties are modified by light. During the past several years, powerful tools such as surface spectroscopic techniques and scanning probe techniques performed on single crystals in ultra-high vacuum, and ultrafast pulsed laser spectroscopic techniques have been brought to bear on these problems, and new insights have become possible. Quantum chemical calculations have also provided new insights. New materials have recently been developed based on titania, and the sensitivity to visible light has improved. The new information available is staggering, but we hope to offer an overview of some of the recent highlights, as well as to review some of the origins and indicate some possible new directions.