The review is aimed at presenting a unified approach in understanding the mechanism of nonequilibrium grain boundary segregation, which can satisfactorily describe the three types of intergranular embrittlement, namely, reverse temper embrittlement of steels, intergranular corrosion embrittlement of stainless steels and intermediate temperature embrittlement of metals and alloys. The review starts with a broad perspective of non-equilibrium grain boundary segregation, including thermally induced non-equilibrium grain boundary segregation and stress induced non-equilibrium grain-boundary segregation. Next, it focuses on the recent progress made in the non-equilibrium grain boundary segregation, including (1) critical time, (2) segregation peak temperature, (3) segregation peak temperature movement for thermally induced and stress induced non-equilibrium grain boundary segregation, and (4) the effect of temperature difference on thermally-induced non-equilibrium grain boundary segregation. Next, the attention is focused on the grain boundary coverage of elements and intergranular embrittlement phenomena. Three types of intergranular embrittlement is analysed in terms of (1) the ductility healing effect induced by the critical time, (2) embrittlement peak or ductility trough induced by the segregation peak temperature, (3) embrittlement peak or ductility trough movement induced by the segregation peak temperature movement and (4) widening and deepening of ductility trough induced by differences in temperature. These experimental phenomena concerning the three types of intergranular embrittlement are consistent with the models of thermally induced and stress induced non-equilibrium grain boundary segregations of impurities, instead of precipitation or equilibrium grain boundary segregation. Towards the end, we visit the subject of grain boundary segregation and associated embrittlement process from the viewpoint of fracture resistance and briefly discuss different perspectives that are of practical significance. List of symbolsA constant b the Burger's vector B Norton coefficient C b (t c ) grain boundary concentration at critical time C b(s50) equilibrium concentration of solute at the grain boundaries C g concentration of solute within the grains C v s~0 ð Þ equilibrium vacancy concentration at grain boundaries C v s~s ð Þ grain boundary vacancy concentration induced by the tensile stress D b the diffusivity D c diffusion coefficients for complexes under or in absence of applied tensile stress D i diffusion coefficients for solute atoms under or in absence of applied tensile stress E the elastic or Young's modulus -E the embrittlement sensitivity in K/at-% of solute at the grain boundary E b formation energy of vacancy solute atom complex International Materials Reviews 2013 VOL 58 NO 5263 E f vacancy formation energy E gb the elastic or Young's modulus of grain boundary region F v the formation energy of a vacancy in the boundary region H Z intergranular Auger peak to peak height of an element normalised with the ...