Abstract: In order to explore the sulfur speciation of coking coal and its transfer laws during prolysis, taking Qinneng coking coal as the study subject, the paper st udied transfer laws of total sulfur and various sulfur speciation in coking coal at pyrolysis temperature 450 ~ 950。C for 30 minutes. The qualitative and semi- quantitativ e analysis of organic sulfide speciation and its relative content were conducted through Fourier transform infrared spectroscopy ( FTIR) and X- ray photoelectron spectr oscopy ( XPS). The results showed that organic sulfide in coking coal could be divided into four categories, including sulfur ether, sulfur oxides, disulfide and Ar- -S typ e sulfide ( aromatic species and thiophene sulfides thiophene) . The total sulfur removal rate was improved mainly due to different kinds of organic sulfide preciptitation during prolysis, iron sulfides was less contributed to total sulfur removal rate. The various kinds of organic sulfide in coal transformed mutually during pyrolysis.