Abstract: TiN/β′-Sialon electroconductive ceramic powder was synthesized by CRN (carbothermal reduction-nitridation) with high-titania slag, bauxite chalmette, silicon fume and carbon black as starting materials. The influences of various reaction parameters such as temperature and holding time at top temperature on the reaction process were studied by XRD, SEM and EDS, as well as the synthesis mechanism. The results showed that the synthetic reaction process of TiN/β′-Sialon powder is greatly affected by the holding time and temperature. The content of β′-Sialon in the sample becomes maximum at 1400°C for 2 hr and these process parameters are regarded as the best during synthesis. At that moment most of β′-Sialon grains in the sample exhibits long and columnar in morphology with fine TiN grains. The volatilization of SiO in the synthesis process results in great mass loss which will further increase with rising temperature and prolonged holding time for a constant temperature.