Ti3(Al1–xSnx)C2 with x = 0.2–0.6 were formed by SHS from Al4C3-adopted samples. TiC-adopted samples were shown to produce Ti3(Al1–ySny)C2 with y = 0.2 and 0.4. Al4C3-adopted samples were exothermic and more beneficial for Sn substitution. A laminated microstructure was composed of plate-like Ti3(Al,Sn)C2 grains.