The depletion of the ore reserves in the world necessitates the search for secondary sources such as waste products (tailings and slag). The treatment and cleaning up of such secondary sources also has a positive impact on the environment. A smelter in Namibia we examined had historic slag which accumulated over decades of its operating life, thus posing the challenge of how best to collect representative samples to evaluate and propose viable methods of recovering contained metals. In this study, analytical and mineralogical characterization of the slag was performed using X-ray fluorescence (XRF) analysis, atomic absorption spectrometer (AAS), ICP-OES, scanning electron microscopy energy dispersive spectroscopy (SEM-EDS) analysis, and optical microscopy analysis. The chemical analyses showed that the metal values contained in the slag were mainly copper, lead, and zinc whose average contents were approximately 0.35% Cu, 3% Pb, and 5.5% Zn. About 10.5% Fe was also contained in the slag. Germanium was detected by scanning electron microscopy, but was however below detection limits of the chemical analysis equipment used. Based on the results, approximate conditions under which the different slag phases were formed were estimated and the recovery routes for the various metals were proposed. Analysis by both optical and scanning electron microscopy revealed that Zn and Fe occurred mainly in association with O as oxides, while Cu and Pb were mainly associated with S as sulphides. The slag consisted of three different phases, namely the silicate phase (slag), metallic phase and the sulphide phases. The phases in the slag were mainly silicate phases as well as metallic and sulphide phases. It was observed that the metallic and sulphide phases were dominant in the finer size fractions (−75 µm) whereas the sulphide phase was also present in the coarser size fractions (+300 µm). An important finding from the microscopy examination was that the sulphide phases were interstitial and could be liberated from the slag. This finding meant that liberation and subsequent concentration of the sulphide phases was feasible using conventional processing techniques.