It has been found that additions of Ti to Nb3Al results in the formation of phases with the B2 crystal structure in as-cast samples. The microstructure and phase stability of two alloys, namely Nb-15Al-10Ti and Nb-15Al-40Ti (in at.%), have been studied. Heat-treatment of the Nb-15Al-10Ti alloy at 1100°C results in the precipitation of an A15 phase in the B2 matrix. A particular orientation relationship exists between the two phases. Heat-treatment above 1600°C results in the dissolution of the second phase. The ALCHEMI technique has been employed to assess qualitatively the distribution of atom types over the two sublattices of the B2 compound.