In this paper, the desulfurization of Fangshan coal was carried out by tetrachloroethylene extraction under ultrasonic and microwave irradiation. The GC-MS analysis of the tetrachloroethylene extraction reveals that organic sulfur in coal can be removed by tetrachloroethylene extract under ultrasonic and microwave irradiation. It is found that microwave irradiation time has great effect on organic sulfur removal. With the microwave irradiation time increases, the efficiency of organic sulfur removal increases. The desulphurization yield reaches maximum, 45%, when the time is 30 minutes or more. It can be clearly seen that Fangshan coal was oxidated by peroxyacetic acid under ultrasonic and microwave irradiation. From the XPS analysis of the macerals of the coal, most of the inorganic sulfur and organic sulfur are removed, especially thioether and thioalcohol which can be completely removed. These results suggest that microwave is an effective way to remove sulfur in coal.