The thermal degradation behaviours of flame-retarded unsaturated polyester resin formulations containing ammonium polyphosphate (APP), Cloisite 25A nanoclay and zinc based smoke suppressants have been studied using thermogravimetric analysis (TGA) combined with infrared analysis of the evolved gases (EGA) and pyrolysis/gas chromatography–mass spectrometry (GC/MS). In TGA–EGA experiments, the mass loss as a function of temperature has been correlated with the evolution of carbon monoxide (CO) and carbon dioxide (CO₂) and oxygen (O₂) consumption as measured by an oxygen analyser. The effect of APP, Cloisite 25A and the smoke suppressants on the evolution of CO and CO₂ has been examined. The decomposition behaviour of flame-retarded polyester resins under isothermal pyrolytic conditions was investigated and the evolved gaseous products were collected and qualitatively and semi-quantitatively analysed via GC/MS. The addition of APP does not yield many new gaseous products relative to the unmodified polyester resin neither does the presence of zinc borate (ZB) and zinc stannate (ZS) together with APP. Possible chemical interactions are discussed in an attempt to explain the observed results.