A model Ni-Bi system has been used to investigate intergranular penetration (IGP) phenomenon. All experiments have been done on Ni 26°<110> bicrystal at 700°C using bismuth vapour condensation as a source of liquid bismuth. Such a procedure results at room temperature in either partial or total Liquid Metal Induced Embrittlement (LMIE) of a unique grain boundary, depending on the duration of liquid Bi / solid Ni contact at 700°C. Auger Electron Spectrometry (AES) and Rutherford Backscattering Spectrometry (RBS) have been used to measure the Bi concentration profile between the source of liquid bismuth and the penetration front. Two zones have been clearly identified : the first one of almost constant Bi concentration called nanometrethick film which is interpreted in terms of Fowler-Guggenheim multi-layer segregation under local equilibrium conditions and the second one with a progressive decrease of Bi concentration over a distance of the order of 20-200μm. Such a long transition zone, together with parabolic diffusion kinetics indicates diffusion-based mechanism of intergranular penetration as opposed to the direct grain boundary wetting.