Thermal methods of various forms have been used to quantify carbonaceous materials. Thermal/optical carbon analysis provides measurements of organic and elemental carbon concentrations as well as fractions evolving at specific temperatures in ambient and source aerosols. Detection of thermally desorbed organic compounds with thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) identifies and quantifies over 100 individual organic compounds in particulate matter (PM) samples. The resulting mass spectra contain information that is consistent among, but different between, source emissions even in the absence of association with specific organic compounds. TD-GC/MS is a demonstrated alternative to solvent extraction for many organic compounds and can be applied to samples from existing networks. It is amenable to field-deployable instruments capable of measuring organic aerosol composition in near real-time. In this review, thermal stability of organic compounds is related to chemical structures, providing a basis for understanding thermochemical properties of carbonaceous aerosols. Recent advances in thermal methods applied to determine aerosol chemical compositions are summarized and their potential for uncovering aerosol chemistry are evaluated. Current limitations and future research needs of the thermal methods are included.