The present work aims to study the relationship among the thermal ageing stability, dynamic properties, cure systems, and antioxidants in natural rubber (NR) vulcanisates. Thermal degradation behavior of NR vulcanisates has been investigated and correlated to the changes in cross-link density, tensile and dynamic mechanical properties. The results obtained show that thermal ageing properties of NR vulcanisates depend strongly on cross-link density, which changes during thermal oxidative ageing or the so-called postcuring effect. In addition, the increases in ageing temperature and time lead dominantly to the postcuring and linkages scission phenomena in vulcanisates cured with CV and EV systems, respectively. With increasing ageing temperature, the tensile strength shows sharp drop at ageing temperature higher than 70 C and 100 C for the specimens cured with CV and EV systems, respectively. The sharp drop of tensile strength of vulcanisates cured with CV system is attributed to the too high cross-link density, which is caused by the postcuring effect. In the case of the vulcanisates cured with EV system, the linkage scission causes the sharp drop of tensile strength. The addition of amine-based antioxidant appears to improve ageing properties. However, the excessive antioxidant reduces tensile properties via a decrease in cross-link density.