Intrinsically ductile metals are prone to catastrophic failure when exposed to certain liquid metals, but the atomic-level mechanism for this effect is not fully understood. We characterized a model system, a nickel sample infused with bismuth atoms, by using aberration-corrected scanning transmission electron microscopy and observed a bilayer interfacial phase that is the underlying cause of embrittlement. This finding provides a new perspective for understanding the atomic-scale embrittlement mechanism and for developing strategies to control the practically important liquid metal embrittlement and the more general grain boundary embrittlement phenomena in alloys. This study further demonstrates that adsorption can induce a coupled grain boundary structural and chemical phase transition that causes drastic changes in properties.