A sol–gel method for the preparation of solid-phase microextraction (SPME) fiber was described and evaluated. The extraction phase of poly(dimethysiloxane) (PDMS) containing 3% vinyl group was physically incorporated into the sol–gel network without chemical bonding. The extraction phase itself is then partly crosslinked at 320°C, forming an independent polymer network and can withstand desorption temperature of 290°C. The headspace extraction of BTX by the fiber SPME was evaluated and the detection limit of o-xylene was down to 0.26ng/l. Extraction and determination of organophosphorus pesticides (OPPs) in water, orange juice and red wine by the SPME-GC thermionic specified detector (TSD) was validated. Limits of detection of the method for OPPs were below 10ng/l except methidathion. Relative standard deviations (RSDs) were in the range of 1–20% for pesticides being tested.