Microstructure evolution and mechanical properties in an Fe-17Cr-4Ni-4Cu alloy aged at 475 °C after different aging times were studied. Conventional transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM) studies revealed the formation of 9R-structure Cu-rich precipitates and Cr-rich α’ phase by spinodal decomposition in the samples aged at 475 °C after 100–1000 h. The fine Cu-rich precipitates and Cr-rich α’ phase by spinodal decomposition lead to a significant increase in the hardness, together in the early stages (100 h). Continued aging to 500 h leads to increased precipitation of the Cr-rich α’, which provides significant strengthening, reaching maximum hardening, despite the continued loss of hardening by weakening by the Ostwald ripening of the Cu-rich precipitates. Extending the aging time to 1000 h leads to substantial reversed austenite transformation and a large number of ripening -copper precipitates that causes softening. The results of the impact tests showed that the major fracture mode was cleavage and/or quasi-cleavage.