An interface and gas chromatograph oven are described that couple a thermogravimetric analyzer with a mass spectrometer and permit multiple capillary gas chromatographic separations of volatile thermal decomposition products generated during a single thermogravimetric analysis. Examples of the use of this apparatus for identifying the volatile products generated during poly(vinyl butyral) thermal decomposition in the presence of γ-alumina and catalytic cracking of poly(styrene) and poly(ethylene) are described. TG-GC/MS analyses employing isothermal, temperature programmed, and subambient temperature ramp gas chromatography separations are described. The apparatus permits repetitive temperature-programmed capillary gas chromatographic analyses of thermogravimetric effluent containing more than 25 constituents in 3-min intervals.