While the primary function of concrete is structural, its pervasiveness in our society lends it to other functions and creates the need for it to maintain its integrity and aesthetic quality. Therefore, concrete with added functionality–for example, self-cleaning characteristics and the ability to remove pollutants–is desirable. Heterogeneous photocatalysis (e.g., gas–solid or liquid–solid catalytic processes caused by light irradiation) by semiconductor particles or coatings has now reached a high level of development and is a promising technology for the reduction of global environmental pollutants. Among the various semiconductor materials, TiO2 in the form of anatase has attracted wide interest, due to its strong oxidizing power under near-UV radiation, its chemical stability when exposed to acidic and basic compounds, its chemical inertness in the absence of UV light, and the absence of toxicity. TiO2 has proved very effective in the reduction of pollutants such as NOx, aromatics, ammonia, and aldehydes. Surprisingly, the use of TiO2 in combination with cementitious materials has shown a favorable synergistic effect in the reduction of pollutants. These new materials have already found relevant applications in self-cleaning building walls and in the reduction of urban pollutants.