Liquid metal embrittlement (LME) of copper by liquid bismuth is investigated at 300◦C. It is shown that a very rapid damage is due to the synergy between the external stress and the phenomenon of intergranular penetration (IGP). Tests of IGP, i.e. without external stress, were done at 300◦C and at 600°C and have resulted in strong intergranular embrittlement due to the formation of nanometer-thick intergranular films, as measured and quantified by Auger electron spectroscopy (AES). The formation of these films is discussed with respect to apparently non-zero dihedral angles at 600°C. A general procedure based on mechanical testing and AES measurements, to check whether IGP has occurred or not, is outlined. This procedure can be seen as an alternative way to determine the wetting transition temperature. The presence of nanometer-thick films due to IGP is discussed with respect to the LME mechanisms.