Formation of nanocrystalline Al3Ti, TiAl, Ti3Al, and Ti5Si3 composites by mechanically alloying (MA) in the Ti–Al–Si system and subsequent annealing treatment are investigated. Microstructure development was monitored by x-ray diffraction, differential thermal analysis, and transmission electron microscopy. An amorphous phase could be generated through milling for 100 h. The results of annealing at different temperatures on this amorphous phase show that the formation of titanium aluminides (Al3Ti, TiAl, and Ti3Al, according to the initial relative amount of Ti and Al) and Ti5Si3 (the only silicide produced by the crystallization reaction) take place. Annealing produces nanocrystalline composites of Al3Ti, TiAl, Ti3Al, and Ti5Si3 with a grain size less than 20 nm. With increasing annealing temperature, the crystalline sizes of the phases increased.