Grain boundary segregation of impurities like P, S, Sb, and others is the origin of temper embrittlement of low-alloy steels. Till now it has been assumed that the segregation is determined by an equilibrium segregation mechanism, but some open questions cannot be satisfactorily explained by the equilibrium segregation mechanism. In the present work, a combined equilibrium and non-equilibrium segregation mechanism of temper embrittlement was established and some open questions on temper embrittlement were addressed by means of the model. The model was applied to phosphorus segregation in an Fe-0.3% C-3.5% Ni-1.7% Cr-0.06% P steel.