The thermal degradation behaviour of nanocomposites based upon poly(propylene)/organoclay, modified with protonated octadecyl amine (C18) in comparison to that of non-exfoliated microcomposites based upon organoclay, modified with protonated butyl amine (C4), was studied by thermogravimetry. In the case of the nanocomposite, the temperature at which volatilisation occurs increases as compared of the microcomposite. Moreover, the thermal oxidation process of the polymer is strongly slowed down in the nanocomposite with high char yield both by a physical barrier effect, enhanced by ablative reassembling of the silicate, and by a chemical catalytic action due to the silicate and to the strongly acid sites created by thermal decomposition of the protonated amine silicate modifier.