Abstract In this work, a highly porous fibre coated with polythiophene/hexagonally ordered silica nanocomposite (PT/SBA-15) was prepared and used for extraction of essential oils with microwave-assisted distillation headspace solid phase microextraction (MA-HS-SPME) method. The prepared nanomaterials were immobilised on a stainless steel wire for fabrication of the SPME fibre. Using MA-HS-SPME followed by GC-MS, 24 compounds were separated and identified in Achillea tenuifolia, which mainly included limonene (28.6%), α-cadinol (12.7%), borneol (6.7%), caryophyllene oxide (3.2%), bornyl acetate (4.3%), camphene (3.2%) and para-cymene (2.3%). The experimental results showed that the polythiophene/hexagonally ordered silica nanocomposite fibres were suitable for the semi-quantitative study of the composition of essential oils in plant materials and for monitoring the variations in the volatile components of the plants.