During operating lifetime of a nuclear power plant, the pressure boundary components, usually in 16MND5 (SA508 Cl. 3) steel, are subjected to thermal aging that may induce phosphorus intergranular segregation. This is known to decrease brittle fracture stress and induce intergranular fracture, which causes reversible temper embrittlement. Large components such as the reactor pressure vessel presents microstructure heterogeneity due to forging and welding. Tempered martensite can locally be found in the nominally bainitic steel. The question of microstructure susceptibility to reversible temper embrittlement has been raised in literature suggesting that tempered martensite has higher sensibility to phosphorus intergranular segregation than tempered bainite. In this paper, a comparative study of intergranular segregation in tempered bainitic and martensitic 16MND5 steel after thermal aging is conducted using energy dispersive X-ray spectroscopy on transmission electron microscope. Focus ion beam is used to precisely prepare lamellae at prior austenite grain boundaries on step cooled bainitic and martensitic samples. Different types of grain boundaries are identified using precession assisted crystal orientation mapping and then the local chemical composition is analyzed. Phosphorus, nickel, manganese and molybdenum were observed at all types of grain boundaries in both microstructures. The segregation levels are higher in prior austenitic grain boundaries than in other types of boundaries for both microstructures. Taking into account the segregation amount in different types of boundaries, the phosphorus bulk depletion is shown negligible. The results show similar segregation levels in the two studied microstructures, indicating that the susceptibility to thermally induced grain boundary segregation between the tempered bainite and tempered martensite is the same.