Using Ti, Al and C powders as starting materials, the effect of intermetallic compound TiAl3 addition on the combustion synthesis of Ti3AlC has been studied. The experiment results show that the main phase of the combustion product involves Ti2AlC and TiC without Ti3AlC, if the molar ratio of Ti, Al, C is equal to 3:1:1. However, the product Ti3AlC is produced by combustion synthesis if a small amount of TiAl3 is added to the starting mixtures without changing the overall stoichiometry. The Ti3AlC becomes the main phase in the final product upon adding 23.5% TiAl3 (mass fraction) in the raw mixtures. The amount of Ti3AlC increases with increasing of addition of TiAl3 in the raw mixtures. The above experimental phenomena were explained through thermodynamic and kinetic analysis.