**Abstract**

Recently, the surface structure effect on photocatalytic activity has gathered increasing attention due to its reported influence on the charge carrier trapping and separation. Detailed control over the surface structure can be achieved by exposing the specific crystal facets. As a result, the photogenerated electrons and holes can be effectively separated between the different facets of semiconductor crystals. TiO2 is the most studied photocatalyst, with the particles exposing {0 0 1}, {1 0 0}, {1 0 1}, {1 1 0}, {1 1 1}, and {1 0 5} crystal facets. The performed studies have shown that the efficiency of the photocatalytic process strongly depends on the nature of the crystal facet exposed at the photocatalyst surface. In this regard, this chapter focuses on the comparison of possible surface-related parameters and photocatalytic activity of anatase, rutile, and brookite polymorphs with exposed different crystal facets. Particularly, computational data on their different possible surface structures are summarized, focusing on the geometry, energy, and possible reconstructions. This is followed by the general description of the hypothetical Wulff constructions and existing stabilization/synthesis strategies. Such an approach could help to further design, simulate, and optimize photocatalyst surface for efficient photoreduction and photooxidation processes.

**Keywords:** crystal facets, computational, titanium dioxide, photocatalysis, crystal growth, surface engineering
