In presence of disinfectants, PAH are remobilized from the coal tar lining of water distribution mains. Reactions of the PAH with chlorine and chlorine dioxide can lead to chlorinated PAH that might show higher mutagenic effects than the parent PAH. The application of the solid‐phase microextraction as a sampling preparation method in combination with a gas chromatographic mass spectrometric device is a reliable and useful method to achieve detection limits in the lower nanogramme‐per‐liter level for PAH and chlorinated PAH. Thus, the reactions of four PAH (anthracene, fluoranthene, fluorene, and phenanthrene) with chlorine and chlorine dioxide under conditions prevalent in drinking water distribution systems could be investigated. In batch experiments with demineralized and drinking water at pH 7, the concentrations of fluoranthene, fluorene, and phenanthrene remained constant, whereas anthracene reacted quantitatively with both disinfectants. In these reactions, no chlorinated products could be detected, only mono‐hydroxyanthracene and anthraquinone were formed. A reaction mechanism for both reaction products is proposed. The results suggest that oxidation is the major pathway of the reaction of PAH with disinfectants in the systems under investigation.