Applications of heterogeneous photocatalytic processes based on semiconductor particles in cement-based materials have received great attention in recent years in enhancing the aesthetic durability of buildings and reducing global environmental pollution. Amongst all, titanium dioxide (TiO2) is the most widely used semiconductor particle in structural materials with photocatalytic activity because of its low cost, chemically stable nature, and absence of toxicity. Utilization of TiO2 in combination with cement-based materials would plunge the concentration of urban pollutants such as NOx. In fact, cementitious composites containing TiO2 have already found applications in self-cleaning buildings, antimicrobial surfaces, and air-purifying structures. This paper aims to present a comprehensive review on TiO2-based photocatalysis cement technology, its practical applications, and research gaps for further progression of cementitious materials with photocatalytic activity.