A new combination system of TG-GC/MS using high resolution TG technique is reported. The present high resolution TG technique is a dynamic rate control (DRC) method that belongs to the controlled rate thermal analysis (CRTA). In this technique, the heating rate of the sample is dynamically and continuously varied in response to changes in the sample’s decomposition rate. In the present study, the performance and applicability of this system is illustrated by using the thermal decomposition of polyimide/polytetrafluoroethylene/graphite (PYPTFE/GR) resin. The presented data demonstrate that this novel feature improves resolution and enhances the accuracy of identification and quantification. It is concluded that the present method gives more detailed information than that obtained from the conventional method, even for materials decomposing through consecutive and close-lying reactions.