Orthorhombic titanium-based Ti2AlNb alloys cannot be used above a temperature limit of about 800°C due to accelerated oxidation and environmental embrittlement. This embrittlement is caused by the high oxygen solubility which deteriorates the mechanical properties. Even if these materials possess an Al content up to ca. 25at.% no protective alumina layer is formed. Instead a non-protective fast growing mixed scale is found. Several attempts have been made to increase their operation temperature e.g. by coatings but none has proven sufficiently protective so far. One new way presented in this paper is to enrich Al in a narrow surface zone by using a powder pack process (aluminization) followed by a fluorination step. Exposure tests at elevated temperature have shown that the aluminized specimens form an alumina layer during exposure in oxidizing environments. Due to the gradient in the Al-concentration interdiffusion with the substrate and the Al-rich diffusion zone occurs which lowers the Al concentration in the diffusion zone. If the Al content drops below a critical value, Ti oxides will also form, which deteriorates the protection provided by the alumina scale. The subsequent fluorination triggers the fluorine effect which stabilizes the protective alumina layer. Untreated specimens are covered with a thick non protective scale and exhibit oxygen ingress in the subsurface zone while treated specimens reveal a thin protective alumina layer and no inward diffusion of oxygen. In this paper results of exposure tests of untreated and treated orthorhombic Ti2AlNb alloys will be presented and compared with the Nb-free α2-phase Ti3Al and Nb-containing Ti3Al-based alloys.