An automated analysis system consisting of a dynamic headspace (DHS) system coupled with thermal desorption-Gas Chromatography/Mass Spectrometry (TD-GC/MS) was used for fully automated micro-scale chamber material emission analysis of Spray Polyurethane Foam (SPF). Closed-cell and open-cell SPF samples were analyzed for emissions of TVOCs and high boiling compounds such as, for example, flame retardants and amine catalyst. Foam samples were analyzed qualitatively, and 15 hour emission tests subsequently carried out to investigate off-gassing mechanisms of the foams. The effect of sample temperature was examined using an automated sequence in which the sample temperature was changed at defined times to simulate the heating of foam insulation in attics or roofs. The experiments provided unattended operation with precise control and documentation of the principal variables in micro-scale chamber experiments: Time, gas flow, and temperature. Samples were subsequently analyzed using the VDA 278 method with direct thermal desorption at 90 °C to determine VOC emissions. Good correlation was obtained between the two methods from a qualitative point of view. Semi-quantitative results were obtained using toluene equivalents.