Clean water and the increased use of renewable energy are considered to be two of the main goals in the effort to achieve a sustainable living environment. The fulfillment of these goals may include the use of solar-driven photocatalytic processes that are found to be quite effective in water purification, as well as hydrogen generation. H₂ production by water splitting and photocatalytic degradation of organic pollutants in water both rely on the formation of electron/hole (e⁻/h⁺) pairs at a semiconducting material upon its excitation by light with sufficient photon energy. Most of the photocatalytic studies involve the use of TiO₂ and well-suited model compounds, either as sacrificial agents or pollutants. However, the wider application of this technology requires the harvesting of a broader spectrum of solar irradiation and the suppression of the recombination of photogenerated charge carriers. These limitations can be overcome by the use of different strategies, among which the focus is put on the creation of heterojunctions with another narrow bandgap semiconductor, which can provide high response in the visible light region. In this review paper, we report the most recent advances in the application of TiO₂ based heterojunction (semiconductor-semiconductor) composites for photocatalytic water treatment and water splitting. This review article is subdivided into two major parts, namely Photocatalytic water treatment and Photocatalytic water splitting, to give a thorough examination of all achieved progress. The first part provides an overview on photocatalytic degradation mechanism principles, followed by the most recent applications for photocatalytic degradation and mineralization of contaminants of emerging concern (CEC), such as pharmaceuticals and pesticides with a critical insight into removal mechanism, while the second part focuses on fabrication of TiO₂-based heterojunctions with carbon-based materials, transition metal oxides, transition metal chalcogenides, and multiple composites that were made of three or more semiconductor materials for photocatalytic water splitting.