Globalization, industrialization, and manufacturing have expanded at an alarming rate over past decades. This has caused a rapid depletion of natural energy sources (such as oil and gas) and the production of tones of wastes polluting the environment, which in turn has imposed negative impact on human health. A promising way to tackle the energy crisis and environmental issues is to substitute traditional fossil fuels with clean and sustainable sources of energy. Among them, solar energy is an inexhaustible and the most environment‐friendly resource, which can be effectively absorbed and utilized via a photocatalysis process for hydrogen production from water splitting and degradation of organic pollutants. Titanium dioxide (TiO
2
) is one of the most extensively studied photocatalytic materials, by virtue of its compatible band‐edge position, physiochemical stability, nontoxicity and low cost. However, its photoactivity is remarkably restricted due to the inefficient light absorption only in the UV region of the solar spectrum, as well as easy recombination of photogenerated electrons/holes. To mitigate these limitations, synergistic combination of electronic and structural strategies has been developed in recent years. In this chapter, we have highlighted TiO
2
‐based photocatalysts with well‐defined electronic structure control and structural design that contribute to significant improvements in vital processes and attributes, such as light absorption in the visible region, charge‐carrier dynamics, high surface area, and enhanced light harvesting. Electronic structure engineering, namely doping and heterostructuring, plays a critical role in improving the kinetics of the charge carriers, that is, the separation of electrons and holes pairs, and the extension of light absorption to visible light region, thereby enhancing the photoefficiency of TiO
2
. The structural design of TiO
2
involves various dimensions and morphologies, which not only augments the specific surface area, but also provides suitable platforms to incorporate other materials for maximizing the photocatalytic efficiency. Furthermore, fundamental understanding of the kinetics and dynamics of photoreactivity and other physicochemical properties is covered. The goal is to provide a comprehensive background toward rational engineering of semiconducting photocatalysts and also a guide for future structural design of nanoscale catalysts for solar‐to‐fuel conversion purposes in pursuit of an exciting future of clean and renewable fuel and environmental remediation.