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 fiber coating, extraction temperature of 80°C, extraction time of 60min, desorption time of 7min at 270°C, addition of 1.5g of NaCl, and the sample volume of 8mL. 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 HS–SPME–GC/MS methodology allowed for the rapid, sensitive, precise, and accurate determination of glycols in the samples of runoff water collected from the airport infrastructures. Next, the presented method has been successfully applied to the analysis of samples collected from different international airports.