High-concentrated sulfur wastewater with sodium and COD （chemical oxygen demand） up to 26000 mg/L from a chemical plant, Jiangsu Province of China has been treated by deposition of natrojarosite in lab. The results indicated that the COD of the wastewater was decreased sharply from 26000 mg/L to 1001 mg/L, with removal rate of COD up to 96% by twice precipitations of natrojarosite and twice oxidation of H202. The treated sulfur wastewater reached the requirement of subsequent biochemical treatment to water quality. The optimal operational parameters should be controlled on pH value between 2.50 and 3.20 and 50 g FeCly6H2O solid added in per liter wastewater. The study provided an experimental basis for pretreatment of high-concentrated sulfur wastewater and proposed a new mineralogical method on treatment of other wastewaters. Depositing process of jarosite and its analogs should be able to be used to treat wastewater from mine and other industries to remove S, Fe and other toxic and harmful elements, such as As, Cr, Hg, Pb, etc. in the water.