Intermetallic gamma titanium aluminides display attractive engineering properties at high temperatures of up to 750 °C. To date, they have been used in low-pressure turbine blades and turbocharger rotors in advanced aircraft and automotive engines. This review summarizes the fundamental information of the Ti–Al system. After providing the development of TiAl alloys, typical phases, microstructures and their characteristics in TiAl alloys, the paper focuses on the effects of alloying elements on the phase boundary shifting, stabilizing effects and strengthening mechanism. The relationships between chemical additions, microstructure evolution and mechanical properties of the alloy are discussed. In parallel, the processing technologies and the common heat treatment methods are described in detail, both of which are applied to optimize the mechanical properties via adjusting microstructures. On this basis, the effects from chemical composition, processing technologies and heat treatments on microstructure, which controls the mechanical properties, can be obtained. It has a certain guiding significance for tailoring the microstructures to gain desired mechanical properties.