In the study, the polyoxometalate-based ionic liquid (POM-IL) was prepared. The prepared nanomaterial was immobilized onto a stainless steel wire for fabrication of the solid phase microextraction (SPME) fiber. The applicability of this coating was assessed employing a laboratory-made SPME device and gas chromatography with mass spectrometry (GC–MS) for the extraction of six triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole, triticonazole, and difenconazole) from the headspace of aqueous samples. A series of parameters that affect the performance of microextraction, such as fiber coating, extraction time, stirring rate, ionic strength, pH, desorption temperature, and desorption time, were thoroughly investigated. In optimum conditions, the repeatability for one fiber (n = 3), expressed as relative standard deviation, was between 4.3% and 8.3% for the test compounds. The detection limits for the studied compounds were between 7 and 40 pgmL−1 .