Cr2AlC ceramics (Cr:Al:C =1:1.2:1 mol.%) were synthesized by powder metallurgical method in argon in the temperature range of 700 to1250°C using Cr, Al and graphite powders as the initial materials. The phase relationships during reaction in the ternary system Cr-Al-C were investigated. The products were characterized by X-ray diffraction (XRD) and differential thermal analysis (DTA). It was found that Cr9Al17, Al8Cr5 and Cr2Al intermediate phases were formed in turn with increase of temperature. Up to 1050°C, with consumption of Cr9Al17 and Al8Cr5 phases completely, the amount of Cr2Al increased significantly. Single phase Cr2AlC with small amount of Cr7C3 was produced until 1250°C. Combined with the results of differential thermal analysis (DTA) and X-ray diffraction (XRD), it is revealed that Cr2AlC phase is formed by the reaction of Cr–Al intermetallic compounds, Cr, Al and graphite. In addition, the reaction equations of the process from 660 to1250°C were given.