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The occurrence of Rb and Cs in coal samples from Iqe coalfield was analyzed by a sequential chemical extraction experiment. Five types of Rb and Cs were determined in the coal: water soluble, ion exchangeable, organic bonded, carbonate, and silicate. The results indicated that the occurrence of Cs is similar with Rb in coal, and nearly all Rb and Cs are distributed in silicate. The occurrence of Rb and Cs is most likely associated with silicate minerals in coal. With the high correlation between Rb, Cs, and K, and the high content of kaolinite and illite in these coal samples, it can be inferred that illite probably is the main carrier of Rb and Cs. Minor amounts of Rb and Cs may also be adsorbed by kaolinite in Iqe coal, and Cs may exist in other states, such as an exchangeable ion.