Polymer/organically modified layered silicate (PLS) nanocomposites are a new class of filled polymers with ultrafine phase dimensions, They offer an outstanding combination of stiffness, strength and weight that is difficult to attain separately from the individual components. Additionally, the nanoscopic phase distribution as well as synergism between polymer and the layered silicate result in additional properties, such as flame retardency, enhanced barrier properties and ablation resistance, which are not observed in either component. These nanocomposites are synthesized by blending the organically modified layered silicate (OLS) into the polymer melt. Thus, understanding the relationship between the molecular structure and the thermal stability (decomposition temperature. rate, and the degradation products) of the organic modification of the layered silicate is critical, During this study, modern thermal analysis techniques combined with infrared spectroscopy and mass spectrometry (TGA-FTIR-MS) were used to obtain information on the thermal stability and degradation products. The effect of chemical variation (alkyl chain length, number of alkyls, and unsaturation) of organic modifiers on the thermal stability of the organically exchanged montmorillonite are discussed. A range of interesting results is observed, however, not all are currently understandable.