AbstractQuantitative pyrolysis gas chromatography studies have been conducted on three grades of cross‐linked polyester resin formulated for improved resistance to surface spread of flame. Pyrolysis temperatures from 723 to 1273 K were used, and these values correspond to ‘surface’ temperatures of materials exposed to heat fluxed of 15–149 kW m–2which are typical of conditions experienced in real fires. Comparison is made with earlier macro studies on the evolution of smoke from plastics materials exposed to similar heat fluxes under an inert atmosphere. There is some correlation between the smoke obscuration data obtained in previous macro studies and the yield of volatile aromatic products evolved on pyrolysis. The presence of flame retardants increases the formation of carbon in the pyrolysis residue and decreases the yield of volatile aromatic products isolated. The results are considered in the context of mechanisms of smoke