Intermetallic γ-TiAl-based alloys are lightweight materials for high-temperature applications, e.g., in the aerospace and automotive industries. They can replace much heavier Ni-based alloys at operating temperatures up to 750 °C. Advanced variants of this alloy class enable processing routes that include hot forming. These alloys consist of three relevant crystallographic phases (γ-TiAl, α2-Ti3Al, βo-TiAl) that transform into each other at different temperatures. For thermo-mechanical treatments as well as for adjusting alloy properties required under service conditions, the knowledge of the thermal expansion behavior of these phases is important. Therefore, thermal expansion coefficients were determined for the relevant phases in a Ti-Al-Nb-Mo alloy for temperatures up to 1100 °C using high-energy X-ray diffraction.