The dynamic variations of molecular structure and properties of natural rubber (NR) during the accelerated storage have been studied. The results showed that, with the prolonging of the storage time, the average molecular weight and the gel content increased, the width index of molecular weight distribution decreased, the gel size increased gradually, but the crosslinking density of gel fluctuated only within a narrow range. Besides, the initial plasticity increased, whereas the plasticity retention index decreased. The studies with thermal analyses and infrared spectroscopy showed that the thermal degradation temperature dropped, the thermal degradation rate increased, and the thermal stability has decreased after the storage of NR. The molecular structure and properties of NR are in a state of dynamic variation during accelerate storage.