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In order to investigate the microstructural evolution during self-propagating high-temperature synthesis (SHS) of Ti-Al powder mixture with an atomic ratio of Ti: Al=1:1, a combustion front quenching method (CFQM) was used for extinguishing the propagating combustion wave, and the microstructures on the quenched sample were observed with scanning electron microscope (SEM) and analyzed with energy dispersive spectrometry (EDS). In addition, the combustion temperature of the reaction was measured, and the phase constituent of the synthesized product was inspected by X-ray diffraction (XRD). The results showed that the combustion reaction started from melting of the Al particles, and the melting resulted in dissolving of the Ti particles and forming of Al3Ti grains. As the Al liquid was depleted, the combustion reaction proceeded through solid-state diffusion between the solid Al3Ti and the solid Ti. This led to the forming of TiAl and Ti3Al diffusing layers. In addition, the combustion reaction is incomplete besides TiAl, there are a large amount of Ti3Al and TiAl3 and a small amount of Ti in the final product. This incompleteness chiefly results from the using of coarser Ti powder.