The thermal degradation of natural rubber (NR) in air at a constant heating rate was studied by using of the thermogravimetry (TG) and thermogravimetry and differential thermal analysis (TG-DTA) simultaneous techniques. It indicates that the temperature of thermal degradation of gel and sol of NR rises linearly along with the increment of the heating rate, whereas the heating rate has little effect on the degree of thermal degradation. Accompanying other side reactions, the thermal degradation of NR is not a simple random chain scission process, and it is an exothermic reaction. The dynamic variation of molecular structure of NR during the thermal degradation was studied using Fourier transform infrared spectroscopy (FTIR). It shows that the products of the thermal degradation of both sol and gel of NR are hydroperoxide, carbonyl, and hydroxyl compounds. The formation of gel makes the temperature of the thermal degradation of NR decrease and the rate of the thermal degradation increase; thus, the thermal stability of NR is reduced. (C) 2000 John Wiley & Sons, Inc.