Traditional liquid -liquid extraction of pesticides consumes large volumes of organic solvent which are hazardous to the operator and is not environment friendly. Solid phase microextraction (SPME) is a solvent less extraction method which is safer to the operator and is environmental friendly. A sol-gel hybrid fibre coating material, poly(dimethylsiloxane)-poly(vinyl alcohol) (PDMS-PVA) was synthesized and used in head space solid phase microextraction (HS-SPME) of chlorpyrifos. The thickness of the synthesised PDMS-PVA fiber coating was 13.5 μm and it is thermally stable up to 400 °C. The PDMS-PVA sol-gel hybrid fiber was also stable to two organic solvents tested; acetonitrile and dichloromethane (1 hour dipping) and showed no significant changes in extraction performance for chlorpyrifos. Extracted chlorpyrifos was analysed using gas chromatography electron capture detector (GC-ECD). Optimum SPME parameters affecting the PDMS-PVA HS-SPME performance namely extraction time (15 min), extraction temperature (50 °C), desorption time (5 min), desorption temperature (260 °C) and stirring rate (120 rpm) were used for extraction. It was found that HSSPME using PDMS-PVA sol-gel fiber gave significantly better extraction performance of chlorpyrifos compared to commercial 100 μm PDMS fiber. The PDMS-PVA fiber showed excellent operational performances such as temperature stability (up to 380 °C), coating lifetime (up to 170 times use) and organic solvent stability. The PDMS-PVA-HS-SPME method showed excellent recovery for chlorpyrifos from tomatoes (98.0 %, 5.9% RSD) at 0.01 μg/g spiked level (5 times lower than maximum residue limit set by European Union).Keywords: sol-gel hybrid, solid phase microextraction, chlorpyrifos, gas chromatography-electron capture detector Abstrak Pengekstrakan cecair -cecair tradisional bagi pestisid menggunakan isipadu pelarut organik yang banyak yang merbahaya kepada operator dan tidak mesra alam. Pengekstrakan mikro fasa pepejal (SPME) adalah teknik pengekstrakan tanpa pelarut yang lebih selamat kepada operator dan mesra alam. Bahan gentian tersalut hibrid sol-gel poli(dimetilsiloksana)-poli(vinil alkohol) (PDMS-PVA) telah disintesis dan digunakan untuk pengekstrakan mikro fasa pepejal ruang kepala (HS-SPME) klorpirifos. Ketebalan PDMS-PVA gentian tersalut yang telah disintesis ialah 13.5 µm dan stabil terma sehingga 400 °C. Gentian hibrid sol-gel PDMS-PVA juga stabil terhadap dua pelarut organik yang diuji, asetonitril dan diklorometana (1 jam celupan) dan tidak menunjukkan perbezaan ketara dalam prestasi pengekstrakan klorpirifos. Klopirifos yang telah diekstrak dianalisis menggunakan kromatografi gas-pengesan penangkapan elektron (GC-ECD). Parameter optimum SPME yang mempengaruhi prestasi PDMS-PVA-HS-SPME iaitu masa pengekstrakan (15 min), suhu pengekstrakan (50 °C), masa penyaherapan (5 min). suhu penyaherapan (260 °C) dan kadar putaran (120 rpm) telah digunakan untuk pengekstrakan. HS-SPME menggunakan gentian sol-gel PDMS-PVA menunjukkan prestasi pengekstrakan yang jauh lebi...