The evolution of precipitates in a Fe–2.5 Cu–1.5 Mn–4.0 Ni–1.0 Al multicomponent ferritic alloy during annealing at 500 °C was systematically investigated by aberration-corrected scanning transmission electron microscopy. The atomic-scale structure and chemistry characterization reveal that primary precipitates with enriched Cu, Ni, Mn and Al originate from continuous growth of B2 ordered domains in the as-quenched alloy. The formation of a Cu-rich body-centered cubic (bcc) phase takes place by the decomposition of the B2 ordered primary phase, which forms a Cu-rich bcc core and ordered B2-Ni(Al,Mn) shell. The B2 shells serve as a buffer layer to moderate the coherent strain and to prohibit the inter-diffusion between the Cu-rich precipitates and bcc-Fe matrix, giving rise to a low coarsening rate of the precipitates. The Cu-rich precipitates experience a structural transformation from bcc to 9R at a critical size of ∼6 nm during long time annealing, corresponding to obvious coarsening of the precipitates and dramatic loss in hardness of the alloy.