Abstract: To analysis the effect of the treating of hydrogen nitrate and microwave on morphologic change of sulfur in high-sulfur coking coal in Shanxi province,using the XPS（X ray photoelectron energy spectrum technology） studied the mode of occurrence and content of sulfur in coal samples after pickling and microwave radiation.The research result shows that after treating in coal sample,the content of inorganic sulfur is 14.2%,most of which is sulphate sulfur;the content of organic sulfur is about 85.8%,main component is thiophenic sulfur.After pickling and radiation,the total removing rate of sulfur is 38.8%,the removing rate of sulfide thiol is 45.1%,and the thiophenic sulfur is 20%,the sulfoxide is 29% respectively,and inorganic sulfur almost total removed.The test indicated that using the pickling and microwave method can effectively reduce the sulfur content in high sulfur coking coal in Shanxi province,the total content of sulfur can removed by 38.8%.