Photocatalysis based technologies have a key role in addressing important challenges of the ecological transition, such as environment remediation and conversion of renewable energies. Photocatalysts can in fact be used in hydrogen (H2) production (e.g., via water splitting or photo-reforming of organic substrates), CO2 reduction, pollution mitigation and water or air remediation via oxidation (photodegradation) of pollutants. Titanium dioxide (TiO2) is a “benchmark” photocatalyst, thanks to many favorable characteristics. We here review the basic knowledge on the charge carrier processes that define the optical and photophysical properties of intrinsic TiO2. We describe the main characteristics and advantages of TiO2 as photocatalyst, followed by a summary of historical facts about its application. Next, the dynamics of photogenerated electrons and holes is reviewed, including energy levels and trapping states, charge separation and charge recombination. A section on optical absorption and optical properties follows, including a discussion on TiO2 photoluminescence and on the effect of molecular oxygen (O2) on radiative recombination. We next summarize the elementary photocatalytic processes in aqueous solution, including the photogeneration of reactive oxygen species (ROS) and the hydrogen evolution reaction. We pinpoint the TiO2 limitations and possible ways to overcome them by discussing some of the “hottest” research trends toward solar hydrogen production, which are classified in two categories: (1) approaches based on the use of engineered TiO2 without any cocatalysts. Discussed topics are highly-reduced “black TiO2”, grey and colored TiO2, surface-engineered anatase nanocrystals; (2) strategies based on heterojunction photocatalysts, where TiO2 is electronically coupled with a different material acting as cocatalyst or as sensitizer. Examples discussed include TiO2 composites or heterostructures with metals (e.g., Pt-TiO2, Au-TiO2), with other metal oxides (e.g., Cu2O, NiO, etc.), direct Z-scheme heterojunctions with g-C3N4 (graphitic carbon nitride) and dye-sensitized TiO2.