Abstract Introduction: Research on the volatile oil composition of Thymus kotschyanus Boiss was conducted by applying mesoporous organosilica based on alkylimidazolium ionic liquid (PMO‐IL) as a fibre coating material via a method referred to as microwaveassisted headspace solid‐phase microextraction (MA‐HS‐SPME). Methodology: This technique entails microwave irradiation of the sample and collection of the volatile sample components. These components are further introduced into a gas chromatography–mass spectrometry (GC–MS) injection port for further analysis. A simplex method was used for the optimisation of three different parameters affecting the efficiency of the extraction. Conclusion: The MA‐HS‐SPME method proved to be the most suitable technique in oil determination and extraction from Thymus kotschyanus owing to its advantageous aspects of cost effectiveness, simplicity and solvent independence.