Semiconducting materials are of great technological importance in electronics industry and environmental remediation due to their ability to generate charge carriers when activated with certain energy. The favorable combination of electronic structure, light absorption properties, charge transport characteristics, and excited lifetimes of some semiconductors has made possible its application as photocatalyst. Although many publications define the fundamental aspects of the semiconductors from different points of view, in this chapter the definition of photocatalytic semiconductor, its structural characteristics, and the requirements to be used as photocatalyst are briefly recalled. In addition, the classification of photocatalytic materials and the mechanism of the photocatalytic process are also reviewed. The advantages and disadvantages of the most used photocatalyst TiO 2 and the second-generation TiO 2 -based materials are also addressed.