Titanium dioxide (TiO2) micro and nano architectures have been intensively studied in the past years because of many varied applications in environmental, energy conversion, and storage fields, such as heterogeneous catalysis, dye-sensitized solar cells, lithium/sodium ion batteries, lithium-sulfur (Li-S) batteries, and bio-nanotechnology, etc. Especially the surface and interface structures in the TiO2 structures play important roles in those applications. This mini review article focuses on TiO2 micro and nano architectures with the prevalent crystal structures (anatase, rutile, brookite, and TiO2(B)), and summarizes major advances in the surface and interface engineering and applications in environmental and electrochemical applications. We present the principles and growth mechanisms of TiO2 nanostructures via different strategies, with an emphasis on rational control of the surface and interface structures. We further discuss the applications of TiO2 micro and nano architectures in photocatalysis, lithium/sodium ion batteries, and Li-S batteries. Throughout the discussion, the relationship between the device performance and the surface structures of TiO2 micro/nano structures will be highlighted. Then we discuss the phase transitions of TiO2 nanostructures and possible strategies of improving the phase stability. The review concludes with a perspective on the current challenges and future research directions.