Off-line microscale chamber measurements of spray polyurethane foam require settings to be changed manually and an analyst to start and stop sampling times. An automated dynamic headspace system was used for on-line, fully automated microscale chamber measurements of SPF. In this way, precise measurement and computerized control of sampling times, volumes, and temperature would be possible. After the system was qualified analytically, timed measurements were carried out automatically over a period of approximately 15 h to understand off-gassing mechanisms of the foams. In a separate experiment, the effect of sample temperature was probed using an automated sequence in which temperatures were changed at defined times to simulate the heating of a foam sample in an attic or ceiling. Both experiments provided unattended and precise control and measurement of the three principle variables in microscale chamber experiments: time, sampling volume, and temperature. The system should prove useful for mathematical modeling and for sharing procedures between researchers.