Grain boundary segregation of phosphorus under a 40 MPa tensile stress at 520 • C in a 0.025 wt.% P-doped 2.25Cr1Mo steel, which has already been thermally equilibrated, is examined using Auger electron spectroscopy. The segregation of phosphorus during stress-ageing has a non-equilibrium characteristic, i.e. it is non-equilibrium segregation. The segregation level first increases with increasing stress-ageing time until about 0.5 h and then diminishes with further increasing stress-ageing time, leading the boundary concentration of phosphorus to return to its thermal equilibrium value after ageing for about 15 h. Therefore, the critical time for this non-equilibrium grain boundary segregation of phosphorus is about 0.5 h at which the segregation is peaked. At this critical time, the boundary concentration of phosphorus is about 20.5 at.%, which is about 4.5 at.% higher than its thermal equilibrium level. Xu's kinetic model for stress-induced grain boundary segregation [T.D. Xu, Philos. Mag. 83 (2003) 889-899; T.D. Xu, B.-Y. Cheng, Prog. Mater. Sci. 49 (2) (2004) 109-208] is used to analyse the experimental results, demonstrating that the measured data may be well simulated by the model.