This chapter discusses the mechanism of photocatalysis processes using nanomaterials and their applications. It also focuses on the different types of nanomaterials used in photocatalysis in terms of their synthesis method, microstructure, and their optical and magnetic properties. A number of photocatalytic materials are synthesized by employing hydrothermal methods, such as titania, silver, grapheme-based catalyst, cadmium and nickel sulfides, mixed metal oxide and rare earth metal oxides. The chapter describes the various phase transitions in photocatalysts, their activity, and the role of lattice parameters in determining the microstructure and consequently the macroscopic properties. The best component to study the phase transitions during photocatalysis is TiO2. Finally, the chapter explains the photocatalytic hydrogen production and CO2 reduction in the presence of photocatalysts under ultraviolet (UV) irradiation or solar light and provides an overreview of the environmental applications of different semiconductor and semiconductor-based heterostructures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.