Pyrometallurgical slags from three Cu-Co smelters (Nkana, Mufulira, Chambishi) in the Copperbelt Province, Zambia, were studied from mineralogical and chemical points of view. The slags were enriched in metals and metalloids, mainly Cu (up to 35 wt.%), Co (up to 2.4 wt.%) and As (up to 3650 ppm). The following primary phases were observed in slags: Ca-Fe silicates (clinopyroxene, olivine) and leucite, oxides (spinel-series phases), ubiquitous silicate glass and sulphide/metallic droplets of various sizes. The presence of glass and skeletal/dendritic crystal shapes indicated rapid cooling of the slag melt. Copper and cobalt were found in low concentrations in the majority of silicates (olivine, clinopyroxene) and oxides, substituting for Fe in their structures (up to 7.15 wt.% CoO in olivine, 4.11 wt.% CuO in spinel). Similarly, up to 0.91 wt.% CoO and 6.90 wt.% CuO were observed in the interstitial glass. Nevertheless, the main carriers of these metals in the slags studied were Cu sulphides (digenite, chalcocite, bornite, chalcopyrite), Co-Fe sulphides (cobaltpentlandite), Co-bearing intermetallic phases ((Fe,Co)2As) and alloys. Weathering features corresponding to the presence of secondary metal-bearing phases, such as malachite (Cu2(CO3)(OH)2), brochantite (Cu4SO4(OH)6) and sphaerocobaltite (CoCO3), were observed on the slag surfaces. They indicate that the slags studied are reactive on contact with water/atmosphere and that their environmental stability and release of potentially harmful metals and metalloids must be evaluated further.