High-purity ternary laminated compound Ti3SiC2 was successfully synthesized by a microwave heating method in the flowing argon for the first time. The mixtures of titanium, silicon, and graphitic carbon (Cgc) or activated carbon (Cac) with different molar ratios were used to investigate the reaction mechanisms. It was confirmed that Ti3SiC2 with high purity of 98 vol.% was achieved without the aids of Al. The optimum experimental parameters were determined as Ti/Si/Cgc having the molar ratio of 3/2.2/2, first holding at 1480°C for 30 min, and subsequent dwelling at 1300°C for 60 min.