A new method has been developed for the determination of antifreeze agents such as ethylene glycol (EG), propylene glycol (PG) and diethylene glycol (DEG) in the samples of airport runoff water. The method is based on headspace solid-phase microextraction (HS-SPME) of target analytes which is coupled with gas chromatography–mass spectrometry (GC–MS). Until now, there was a lack of appropriate methodology for collecting reliable data about the concentration levels of these toxic de/anti-icing substances in the new type of environmental samples such as the airport runoff water. The evaluation of green extraction technique, i.e. HS-SPME resulted in establishing the optimal extraction conditions, as follows: 85-μm PA fibre coating, extraction temperature of 80 °C, extraction time of 60 min, desorption time of 7 min at 270 °C, addition of 1.5 g of NaCl, and the sample volume of 8 mL. The recovery ranged from 67 to 89%, which demonstrates that the HS-SPME technique is a powerful method for extracting antifreeze agents from the airport stormwater samples. The developed