Liquid metal embrittlement (LME) occurs in some solid–liquid metal elements’ couples (e.g., Fe-Zn and Al-Ga), called specificity. Although some material parameters like solubility and bonding energy were suggested as controlling factors, none could be attributed satisfactorily. Here we have unveiled the primary factor that governs the specificity of LME. From first-principles calculations compared with a systematic surveillance test result, we found that the grain-boundary (GB) adsorption energy shows near-zero values in all embrittling couples; the interaction between solid and liquid metal atoms is weak when an atom from the liquid state penetrates the grain boundary of the solid. Furthermore, we found that the calculated surface adsorption energy that promotes bond-breaking does not correlate to the specificity. Therefore, we consider that the penetration of a liquid metal atom surrounded by weakly interacting solid metal atoms is necessary before the bond-breaking assisted by surface adsorption occurs at a microcrack tip. This mechanism is also applicable for transgranular cracking along low-energy boundaries and crystal planes. While liquid metal atoms penetrate and diffuse into solid GB macroscopically before cracking, liquid metal’s surface adsorption stronger than GB adsorption should promote the bond-breaking of solid metal. In conclusion, the atomistic penetration precedes the surface-adsorption-assisted bond-breaking and controls the specificity of LME.