Poly(methyl methacrylate)–clay nanocomposites have been studied using X-ray photoelectron spectroscopy. It is clear that as the polymer undergoes thermal degradation, the clay accumulates at the surface and the barrier properties which result from this clay accumulation have been described as the reason for the decreased heat release rate for nanocomposites. The surface composition of the clay changes as the nanocomposite is heated and the changes are affected by the organic-modification that were applied to the clay in order to prepare the nanocomposite