Forms of arsenic in a Chinese bituminous coal, Yima, and their transformation behaviors during coal pyrolysis were investigated. The chemical leaching method was used to characterize the forms of arsenic in the raw coal and the chars. The effect of minerals on arsenic release was also studied. It was found that about 72% arsenic in YM coal is bound to sulfide species; 16% to sulfates, phosphates, or oxides; 10% to organic species; and 2% to aluminosilicates. The organic-bound arsenic is the most releasable, while the aluminosilicates-bound arsenic is the least releasable. Aluminosilicates inhibit arsenic release due to the formation of aluminosilicates-bound arsenic during pyrolysis. Sulfides, sulfates, phosphates, or oxides may also restrain arsenic release. Carbonates and ion exchangeable minerals in Yima coal do not show any significant influence on the release of arsenic during coal pyrolysis. Secondary reactions between arsenic and the coal matrix should exist, as evidenced by significant increase in organic-bound arsenic in chars obtained from pyrolysis in a temperature range of 300-700 degrees C.