The development of modern building materials science involves the process of designing innovative materials that exhibit unique characteristics, such as energy efficiency, environmental friendliness, self-healing ability, and photocatalytic properties. This can be achieved by modifying cement with nano- and fine-dispersed additives that can give the material new properties. Such additives include a number of compounds based on the TiO2-Bi2O3 system. These compounds have photocatalytic activity in the near-UV and visible range of the spectrum, which can serve to create photocatalytic concretes. Here, the purpose of this scientific study was to synthesize compounds based on the TiO2-Bi2O3 system using two methods in order to identify the most optimal variant for creating a composite material and determine its properties. Within the framework of this article, two methods of obtaining a photocatalytically active additive based on the TiO2-Bi2O3 system are considered: the solid-state and citrate-based methods. The photocatalytic, mechanical and structural properties of composites containing the synthesized additive are investigated. In this study, it was found that for the creation of photocatalytic concretes, it is advisable to use cement compositions with a bismuth titanate content of 3–10 wt.%. of the cement content, regardless of the method of obtaining the additive. However, the most optimal composition is one containing 5 wt.% of the synthesized additive. It is noted that compositions containing 5% by weight of bismuth titanate demonstrate photocatalytic activity and also show an increase in strength on the first day of hardening by 10% for the solid-state method and 16% for the citrate method.