Various methods are used for the characterization of manufactured and natural polymers. Crucial among these techniques are thermal methods, with thermal gravimetric analysis (TGA) often being the 1st step in polymer characterization. Yet, TGA, as the name implies, is based on gravimetry and thus no chemical structural information is obtained. This presentation will demonstrate the development of thermal methods providing insight into material’s chemical structure along with thermal characteristics. Thermal carbon analysis (TCA), a novel method that enables fast quantification and thermal fractionation of carbonaceous constituents, is complemented by evolved gas analysis with mass spectrometry (EGA-MS). These screening methods are then followed by detailed characterization utilizing thermal desorption pyrolysis GC-MS (TD-Py-GC-MS), which provides identification of breakdown products resulting from individual temperature steps. Together, these thermal methods provide detailed structural information along with structural characteristics for a variety of materials, including plastics such as polystyrene or polypropylene, polyurethanes, hydroxyl-terminated polybutadiene used as rocket fuel, perfluorinated plastics.