Abstract Microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) and PDMS fibers were applied as a single step before determination of polycyclic aromatic hydrocarbon (PAH) concentrations in water using gas chromatography–mass spectrometry (GC-MS). PDMS/DVB was found better in performance and was chosen for the rest of the investigations. Dissolved organic matter (DOM) was found to not effect PAH analysis significantly. This study (MA-HS-SPME) presents the first finding in the literature that total (both freely dissolved and DOM-associated) PAH concentration was determined. To optimize the extraction efficiency of PAHs by MA-HS-SPME, influence of various parameters, including fibers, temperature, duration of thermal desorption, microwave irradiation power and duration, and the temperature of the circulating cooling water system, was studied. Under optimal operating conditions, good linearity of a calibration curve was observed over the st...