We report on a comparative measurement of intergranular bismuth coverage on a copper substrate using Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectroscopy (RBS). Bicrystalline copper samples were put in presence of bismuth vapour at 500 ∞C (consequently embrittled by the grain-boundary penetration of Bi atoms), water-quenched and subsequently fractured at room temperature. Each fracture surface was analysed by AES, XPS and RBS with the help of quantitative procedures developed for each of the three techniques. All possible sources of discrepancy were carefully examined. The combined quantitative approaches have led to excellent agreement. Such a good agreement constitutes a necessary condition to begin a critical discussion on the mechanisms potentially involved in the liquid metal embrittlement (LME) phenomenon. Copyright © 2005 John Wiley & Sons, Ltd.