•Using multi-scale testing experiments to distinguish the aging mechanism and performance transformation.•Molecular dynamics simulation is carried out to explore the microscopic mechanism of the aging property transformation.•Corresponding relationship between macroscopic and microscopic performance is determined through comparative analysis. As a complex mixed system, the aging mechanism of high-energy composite materials involves the aging of each component itself, interactions between components, and transformation of microstructural and thermodynamic properties. The study of a single component or performance parameter has great limitations for elaborating the cognitive complexity of aging processes, making it difficult to reveal the underlying principles of physicochemical property transformation. Thus, it can only be applied as an empirical summary. In view of this, this study comprehensively utilized numerical analysis and experimental detection to explore the evolution of micromolecular conformation and changes in macro aging performance from four aspects of composite systems, including binder aging, plasticizer migration, bond interface debonding, and mechanical property transformation. There was good consistency observed between molecular simulation and thermal aging experiments, indicating that there was basically no post curing process for HTPB propellants using TDI as the curing agent. In the early stage of aging, scission chain was the main process and, in the later stage of aging, oxidation crosslinking the main process. Oxidative crosslinking increased the mean square radius of gyration and glass transition temperature of the binder system, reduced the peak value of radial distribution function, and revealed the reason for the change of propellant hardness and CC and CO double bond content. However, chain degradation increased the number of polar groups, enhanced intermolecular polarity, reduced the solubility parameter, and increased the free volume fraction of the mixed system and the dioctyl sebacate diffusion coefficient. This resulted in an increase in the tangent value of the HTPB propellant loss angle from 0.43 to 0.44° and a decrease in the glass transition temperature from 203.3 to 202.0 K. The binding energy at the interfaces of AP/HTPB and Al/HTPB increased first and then decreased, which was consistent with SEM images of bonding interfaces. The joint effect of binding energy and mechanical properties of the binder system promoted the transformation of the stress-strain curve of aging propellant.