The presence forms of sulfur in High-sulfur petroleum coke and high temperature transfer was studied in this paper. It was found that a part of sulfur escape in the form of gaseous compounds through heating coke without air. The present structure of sulfide is inferred to be thiophene according to XPS spectra. The scientific calculation for amount of high sulfur petroleum coke can be continued according to the sulfur content of petroleum coke, sulfur transfer agent and permissible content of sulfur in the coke. The gaseous sulfur caused by the high sulfur petroleum coke which is directly used as boiler fuel and coal blending can be recycled through the original sulfur purification recovery system, meanwhile, the purification load rises.