Abstract Phosphorus could be detected at prior austenite grain boundaries (PAGB) in high-strength alloy steels quenched and tempered at 500°C when using a VG's HB 501 dedicated field emission STEM but not with a conventional JEOL 4000FX STEM. No phosphorus was detected at PAGB's in the as-quenched materials or away from PAGB's in tempered materials of either type. The grain boundary coverage of phosphorus was, assuming a specimen thickness of 80 nm, 0.7 monolayers for the 3.5NiCrMoV rotor steel and 0.4 monolayers for the AISI 4340 steel. The grain boundary concentration of phosphorus, assuming a specimen thickness of 80 nm and a segregated layer thickness of 1 nm, for the 3.5NiCrMoV rotor steel was 6 wt% and for AISI 4340 4 wt%. Compared to the bulk concentration of about 0.01 wt% this means that the enrichment factor of P to the grain boundaries was several hundred times (610 respectively 370). Our measurements showed no correlation between the stress corrosion crack growth rate and the grain boundary phosphorus concentration. The yield strength, however, decreased after tempering while the phosphorus concentration at the grain boundaries increased.