In this work, the original BCR extraction scheme was modified and applied to study the partitioning of metals in fly ashes. In the first step, the water-soluble fraction was investigated here. The next metal fractions were acid-soluble, reducible, and oxidisable. Two kinds of coal fly ash certified reference materials were analysed. Metal concentrations in the extracts were measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). The efficiency of the extraction process for each step was examined. The partitioning of metals between the individual fractions was investigated and is discussed.