The enrichment mechanisms of precious metals by base metals or their mattes in pyrometallurgical processes are discussed at the atomic level in this paper. The reasons brought forward for a trace amount of precious metals to be trapped into base metals or mattes are that the melted slag phases possess different chemical structures and properties from that of the melted base metal or matte phases. As for the melted slag phase, its formation is thought to depend on the covalent bonds and the ionic bonds between Si, O atoms and Ca2+, Mg2+, Fe2+ ions to tie up each other. Because the bridging electrons in the slag phase are all thought as the localized electrons, the precious metal atoms are not stable among them. However, as for the metal phase, its formation is thought depend on the metal bonds to bind up the metal atoms. Because the electrons in the metal phases can move freely among the atoms, the precious metal atoms that enter the metal phase can cause the system’s free energy to decrease. For the melted mattes phase，because it has high electrical conductivities (between 103～104 s·cm-1) at higher temperatures, and its temperature coefficients presents the negative values, its conductance mechanism belongs with the electronic conduction. The property of the mattes is in fact similar to that of the metal at their melted state, so the precious metal atoms will enter the matte phase instead of the slag phase in a mattesmelting process.