Historical slags from the past Fe and Cu-Co production were investigated in order to evaluate either their potential for utilization or their long-term environmental risk for unsupervised old smelting areas. Here, we studied ferrous slags produced during the recovery of Fe from siderite-Cu ores in Slovakia and two different types of non-ferrous slags produced during the recovery of Cu and Co from Kupferschiefer ores in Germany. The glassy character, rare occurrence of primary silicate phases, and the lack of secondary phases in Cu slags indicate their stability for a prolonged period of time. Electron microprobe analytical work showed that the metals and metalloids (Cu, Co, Fe, Zn, Pb, As) are largely encased in droplets of matte and metal alloys and remain protected by the glassy matrix with its low weathering rate. Fe and Co slags are composed of high-temperature silicates such as wollastonite, cristobalite, as well as olivine, feldspar, quartz, leucite, pyroxene, and pyroxenoids. The presence of secondary phases attests to a certain degree metal release owing to weathering. Assuming minimal contents of metals in slags after a treatment with dilute H2SO4, slags could be used as pozzolanas for addition to cement.