Abstract The formation and stability of Al-rich Ti–Al phases is reviewed and the kinetics of the phase transformations and evolution of lamellar TiAl + r-TiAl 2 microstructures is discussed. For this a couple of Ti–60 at.% Al alloys were processed by different techniques to generate different initial microstructures. The kinetics were studied by annealing the differently processed alloys for 1, 10, 100 and 1000 h at temperatures between 800 and 1000 °C and then analysing the quenched microstructures by optical, scanning electron, and transmission electron microscopy. In addition, in situ heating and cooling experiments using differential thermal analysis and transmission electron microscopy were performed to verify the results obtained for the quenched samples. The results conclusively show why the metastable phases h-TiAl 2 and Ti 3 Al 5 form. The stability and transformation of the metastable phases have been determined in dependence on time and temperature and the kinetics of the two different mechanisms by which the stable phase r-TiAl 2 forms have been established. The effects of differing initial microstructures on the evolution of the microstructure with time and temperature are discussed.