TiO2 has been intensively investigated for decades as the most important photocatalyst, but its photoactivity still needs further improvment. TiO2 surface and interface are vital in photocatalysis because it is where the photo-excitation, charge transfer and subsequent photoreaction take place. Surface and interface control has been demonstrated as very effective approach to synthesize highly efficient TiO2. Here we highlight our recent work as well as the state-of-the-art in controlling of TiO2 surface and interface including facet growth, surface decoration and surface adsorption that leads to better photocatalytic performance. It is expected to provide some guidelines for rational design and fabrication of highly efficient TiO2-based materials for photocatalysis.