Combustion synthesis (CS) of Si3N4 was accomplished by using as-milled Si/NH4Cl as reactants at low nitrogen pressure. The additive of NH4Cl decreased the combustion temperature and promoted the Si nitridation. Full nitridation of Si was achieved by burning Si in pressurized nitrogen with 10 ~ 25 wt. % NH4Cl as additives while no Si3N4 diluent added. The maximum combustion temperature (Tc), the combustion velocity (u) together with the α-Si3N4 content and mean particle size (d50) of the powder products were found to be great dependent on the NH4Cl content added in the reactants. Fine Si3N4 powder products with α-phase content up to 85 wt. % were obtained via steady combustion mode. A mathematical approach named combustion wave velocity methods for the analysis of temperature profiles in CS was proposed and the reaction kinetics was discussed. The apparent activation energy calculated according to the temperature profile analysis method is 29.7 kJ/mol, which agrees well with the corresponding low temperature nitriding combustion of Si.