The segregation behavior of phosphorus (P) in the heat-affected zone (HAZ) of an A533B/A182 dissimilar weld joint before and after step cooling was investigated with atom probe tomography. At grain/packet boundaries, the final P segregation level consisted of non-equilibrium segregation that occurred during cooling after welding and post-weld heat treatment (PWHT) and equilibrium segregation that occurred during step cooling. In both processes, higher P coverage was observed in the coarse-grained and intercritically reheated coarse-grained HAZ than in the fine-grained HAZ and base material. The cooling after welding and PWHT seemed to have a pronounced impact on P segregation in the subsequent aging process. In addition, P segregation also occurred at the precipitate/matrix interfaces of cementite, Mo2C and Al-Si rich precipitates. The evolution of P coverage at these two types of sites suggested increasing risks of embrittlement with an increase in aging time.