Powder production by gas atomization of γ-TiAl based alloys typically yields a highly nonequilibrium material regarding the occurring phases and their microstructural appearance. In particular, the equilibration of the powder and the associated phase transformations during heating are of great importance for the subsequently applied densification techniques. The present work employs in situ high-energy X-ray diffraction to investigate how this thermodynamic equilibration manifests itself in the resulting phase distribution, the ordering behavior of the disordered α and β phase, both evidenced in the powder, and the change of the γ lattice parameters during heating of a Ti–46.3Al–2.2W–0.2B (at%) powder up to 850 °C. Complementary microstructural characterization of the gas-atomized powder and the heat-treated material condition reveals that the temperature exposure predominately affects the dendritic parts of the microstructure, especially when the α phase is transformed into γ phase with small embedded grains of α2 and βo.