Thermal decompositions of polyisoprene, poly(p-isopropyl α-methylstyrene) (PPIPαMS), and poly(isoprene/p-isopropyl α-methylstyrene) (sample M-32) were carried out at various temperatures in the range 200–340° C in a differential thermo-gravimetric apparatus. The undecomposed polymers as well as their decomposed residues were analyzed by gel-permeation chromatography (GPC), infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Based on the changes observed in the distribution of molecular weights, depolymerization is the predominant step in the decomposition of PPIPAMS and polymer M-32, whereas random scissions predominate in the case of polyisoprene. The combined data of GPC, IR, and NMR indicate that only interchain reactions leading to the formation of cyclized products are present in the decomposition of polyisoprene while interchain as well as intrachain reactions are operative in the case of polymer M-32.