High‐purity titanium aluminum carbide (Ti3AlC2) powders were synthesized by a microwave sintering method using different titanium sources as raw materials. The prepared products were characterized by differential scanning calorimetry (DSC), X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicated that the synthesized Ti3AlC2 powders have high purity (97.5%) and even distribution of the grain size when using a 3TiH2/1.2Al/2C mixture as raw materials when the microwave sintering temperature and time were 1300°C and 30 minutes, respectively. The formation mechanism of the Ti3AlC2 is described as proceeding via four stages. The solid‐phase reaction between titanium and aluminum occurs below the melting point of aluminum and the main product is a Ti3Al phase, which is an observed intermediate compound for the formation of Ti2AlC and Ti3AlC2. Thus, this study provides a beneficial approach to low‐temperature synthesis of high‐purity Ti3AlC2 materials. [ABSTRACT FROM AUTHOR]