Ultrafine β-sialon powder is synthesized by citrate sol-gel and carbothermal reduction and nitridation (CRN) process. The presence of small amounts of β-sialon as crystal seed can obviously accelerate the formation of final β-sialon product and lower its formation temperature. The effects of nitriding temperature on the formation of the final β-sialon are investigated. The mean particle size of the prepared β-sialon powder is 100 ~ 150 nm. The β-sialon precursor gel and the ultrafine β-sialon powder are characterized by XRD, TG-DTA and SEM. The isoelectric point of ultrafine β-sialon is pH 2.46.