Abstract: This paper deals with cherubal stole of sulfur in add Whier generated form weathered wastestone of Dexing Copper Mine.The spectral distribution was scanned by double crystal X-ray fluoescence spcetrometer and analysed by SULS program which was set up on the beds of the principle of nonlinear least sqiare. According to the analytical results of the samples of known sulfur speciation, the relative error was less than 6% for S^2- and S⁰, and less than 16% for S⁴⁺ and S⁶⁺. This result is comparable with that obtained by infrared and chemical methods,the relatively analytical error of which was less than 15%.On the basis of tile analytical results it is considered that there were two speciess of sulfur in the acid water generated from the weathered wastestone of Dexing Copper Mine. The concentration of tetravalent sulfur in the acid water which was just flown off the wastestone dump was amounted to 72% of total silfur.