Pd(0) is able to catalyze oxygen-involving reactions because of its capability to convert molecular oxygen to the very reactive atomic form. Consequently, the embedding of a little amount of Pd(0) clusters in polymeric phases can be technologically exploited to enhance the incineration kinetic of these polymers. The effect of nanostructuration on the Pd(0) catalytic activity in the polymer incineration reaction has been studied using poly( N -vinyl-2-pyrrolidone) ( Mw ¯  = 10,000 gmol −1 ) as polymeric model system. A change in the PVP incineration kinetic mechanism with significant increase in the reaction rate was experimentally found. The kinetic of the Pd(0)-catalyzed combustion has been studied by isothermal thermogravimetric analysis. After a short induction time, the combustion in presence of Pd(0) clusters shifted to a zero-order kinetic from a second-order kinetic control, which is operative in pure PVP combustion reaction. In addition, the activation energy resulted much lowered compared to the pure PVP incineration case (from 300 to 260 kJ/mol).