Studies of thermal and fire-resistant properties of the polypropylene/multi-walled carbon nanotube composites (PP/MWCNT) prepared by means of melt intercalation are discussed. The sets of the data acquired with the aid of non-isothermal TG experiments have been treated by the model kinetic analysis. The thermal-oxidative degradation behavior of PP/MWCNT and stabilizing effect caused by addition of MWCNT has been investigated by means of TGA and EPR spectroscopy. The results of cone calorimetric tests lead to the conclusion that char formation plays a key role in the mechanism of flame retardation for nanocomposites. This could be explained by the specific antioxidant properties and high thermal conductivity of MWCNT which determine high-performance carbonization during thermal degradation process. Comparative analysis of the flammability characteristics for PP-clay/MWCNT nanocomposites was provided in order to emphasize the specific behavior of the nanocomposites under high-temperature tests.