Challenging issues concerning energy efficiency and environmental politics require novel approaches to materials design. A recent example with regard to structural materials is the emergence of lightweight intermetallic TiAl alloys. Their excellent high-temperature mechanical properties, low density and high stiffness constitute a profile perfectly suitable for their application as advanced aero-engine turbine blades or as turbocharger turbine wheels in next-generation automotive engines. As the properties of TiAl alloys during processing as well as during service are dependent on the phases occurring, detailed knowledge of their volume fractions and distribution within the microstructure is of paramount importance. Furthermore, the behavior of the individual phases during hot deformation and subsequent heat treatments is of interest to define reliable and cost-effective industrial production processes. In situ high-energy X-ray diffraction methods allow tracing the evolution of phase fractions over a large temperature range. Neutron diffraction unveils information on order-disorder transformations in TiAl alloys. Small-angle scattering experiments offer insights into the materials’ precipitation behavior. This review attempts to shine a light on selected in situ diffraction and scattering techniques and the ways in which they promoted the development of an advanced engineering TiAl alloy.