Coal fly ash, which is a source of metals emission to environment, was researched. Investigations on Cr chemical fractions and their environmental mobility in ash–solution system were carried out. In order to obtain results repeatedly, the conditions of sequential extraction of Cr from coal fly ash were optimized. It was found that Cr in coal fly ash occurs in the following fractions (mg kg−1): exchangeable (2.5), associated to carbonates (4.0), associated to organic matter and sulfides (8.5), associated to Fe–Mn oxides (16.0), and residual (41.6). Mobility fractions of Cr contain 8.2% of its total concentration in the fly ash in environmental conditions. The obtained results indicate that coal fly ash is a source of environmental contamination by Cr especially, in soils where its utilization is inadequate.