The thermal stability of organically modified layered silicate (OLS) plays a key role in the synthesis and processing of polymer-layered silicate (PLS) nanocomposites. The nonoxidative thermal degradation of montmorillonite and alkyl quaternary ammonium-modified montmorillonite were examined using conventional and high-resolution TGA combined with Fourier transform infrared spectroscopy and mass spectrometry (TG−FTIR−MS) and pyrolysis/GC−MS. The onset temperature of decomposition of these OLSs was approximately 155 °C via TGA and 180 °C via TGA−MS, where TGA−MS enables the differentiation of water desorbtion from true organic decomposition. Analysis of products (GC−MS) indicates that the initial degradation of the surfactant in the OLS follows a Hoffmann elimination reaction and that the architecture (trimethyl or dimethyl), chain length, surfactant mixture, exchanged ratio, or preconditioning (washing) does not alter the initial onset temperatures. Catalytic sites on the aluminosilicate layer reduce ther...