The kaolinite-polyacrylamide intercalation compound was prepared by the displacement reaction of the kaolinite-formamide intercalation precursor with acrylamide and the polymerization under 140°C for 15h with the catalysis of dibenzoyl peroxide. Sialon was synthesized from kaolinite-polyacrylamide intercalation compound by carbothermal reduction and nitridation (CRN) processing at 1400°C. The kaolinite-carbon mixture and its CRN product were also prepared for the comparison with the CRN result of intercalation compound. XRD, FT-IR, and TEM were used to characterize the phases, structure and morphology of products. In the CRN product from the intercalation compound, β′-sialon is the main phase. And the reduction and nitridation rate from the intercalation compound was greater than that from the mixture. There was higher sialon phase’s content and lower mullite phase’s content in the CRN product from the intercalation compound than that from the mixture. The CRN processing of kaolinite intercalation compound is a novel and effective method of sialon synthesis.