Migration of styrene from thermoset polyester cookware into foods has been studied during normal cooking applications and for the fatty food simulant olive oil under high temperature test conditions. The analysis of foods was by automated headspace gas chromatography/mass spectrometry (GC/MS) in the selected ion mode. Cyclohexane was added to the slurried foods to improve headspace partition and deuterated‐styrene was the internal standard. To achieve adequate sensitivity with olive oil, styrene was extracted and concentrated by a steam distillation method and then determined by GC/MS. Styrene in foods cooked in thermoset polyester articles was in the range <5 to 5μg/kg and 5 to 30μg/kg where the polyester contained 9 and 380 mg/kg residual monomer respectively. Testing for 2 h at 175°C into olive oil resulted in significantly higher migration of styrene than seen for other foods, although there was a marked decrease in migration on repeatuse. Testing of the complete articles as sealed systems filled with olive oil led to higher migration than testing by total immersion of plaques. Of the test methods used with olive oil, testing as filled articles with no lidding gave migration results closest to (but generally higher than) those seen for real foods.