After solid solution at 850 °C, the Custom 455 was aged at 420 °C for different times. The hardness changes were measured using a Vickers hardness tester, and the microstructure and composition of the second phase were studied using atom probe tomography (APT) and high-resolution transmission electron microscopy (HRTEM). The APT results indicate that in the early stage of aging, Cu atoms first segregate and attract Ti to form CuTi clusters; As the aging time increases, Ti atoms in CuTi clusters attract Ni and form CuTiNi clusters, resulting in a rapid increase in sample hardness; Subsequently, CuNiTi clusters grew and gradually separated into Cu-rich and NiTi-rich particles; As the aging time further increases, some NiTi-rich particles grow into rod-shaped Ni 3 Ti precipitates, while others have Si atoms and grow into spherical G phase particles. The orientation relationship between Cu-rich phase, Ni 3 Ti phase, and G phase is: [100] M //[0–11] Cu //[-12–10] Ni3Ti //[100] G , (011) M //(111) Cu //(0004) Ni3Ti //(022) G . The formation of the Cu-rich, Ni 3 Ti, and G phase resulted in a hardness peak of 538 HV after 16 h of aging. Subsequently, the decrease in hardness caused by the coarsening of the Cu-rich and Ni 3 Ti particles was offset by the newly formed G phase, resulting in a slow decrease in hardness.