The dense cross-linked network not only endows epoxy thermosets with excellent performance in service time but also increases the difficulty of recycling after the end of life. A great deal of research has been dedicated to developing new methods for chemcycling epoxy thermosets. However, they are always case studies within specific types of curing agents, and it lacks understanding of the comprehensive linkage among structure, performance, and recyclability of the thermosets. Herein, we explore the relationship between service performance and oxidative recovery of widely used types of amine-cured epoxy thermosets. Besides, it is also found that the early degradation stages are mainly determined by the grades of carbon linked to the amine in the curing agent, while the mid−late stages are mainly controlled by the cross-link density. This study will provide a useful guide to the service life and recycling of amine-cured epoxy thermosets.