Solute segregation in the carbon-depleted (CDZ) heat-affected zone of dissimilar metal welds (DMW) designed for nuclear power plant EPR TM reactors has been investigated by atom probe tomography (APT) and related to the mechanical properties (toughness test). The analysis of grain boundaries (GBs) by APT allowed the quantification of the P segregation and other solute elements, in all the analyzed samples, before and after long-term ageing heat treatments. The post-weld stress-relief heat treatment applied to the samples before the ageing heat treatments leads to important GBs segregation levels. Following thermal ageing treatments allow a relative increase of GB segregation. P segregation increases with the various thermal ageing conditions. The experimental data were used to model P segregation in high-angle GBs. The simulations show that P segregation is kinetically limited by bulk diffusion, explaining the observed P segregation increase with temperature. P segregation in GBs in the CDZ of the DMW should remain low compared to the expected equilibrium segregation level during the entire reactor service. In addition to solute segregation in extended defects, APT measurements revealed the presence of Cu-rich clusters in GBs, dislocations, and grains in all the aged samples. These clusters were not observed in the sample before ageing.