This study aims to contribute to the characterization of Katangese Copperbelt’s (DR Congo) mining wastes and soils polluted with trace metals, using pollution indices and direct concentration measurements. This study also evaluated the use of these indices in assessing the success of remediation projects. Data from previous studies and samples collected from six types of discharge and one polluted soil were used to address the first objective. Soil and plant samples were collected at Kipushi and Penga Penga for the second objective. The results reveal very high concentrations of As, Cd, Co, Cu, Mn, Pb, and Zn in all mine tailings and polluted soils, compared with local references. The degree of contamination (DC) values (from 72 to 5440) and potential ecological risk (RI) values (from 549 to 162,091) indicate very high-risk situations associated with polluted discharges and soils. Regarding revegetation trials, the results show lower concentrations and RIs in tree rhizospheres compared with unamended areas at both sites. However, trace metal concentrations are higher in tree rhizospheres compared with local references, and RI values are in the considerable risk range for Penga Penga (RI = 533) and in the very high range (>1500) for Kipushi. Bioconcentration factor values are below 1, indicating low accumulation in roots, wood, and leaves, and low risk of contamination of the trophic chain. In this context, it seems that the pollution indices used are suitable for characterizing pollution and prioritization for remediation. However, there seems unsuitable for assessing the effectiveness of phytotechnology processes based on metal stabilization. Direct plant performance measurements combined with direct measurements of metals in substrates and plants to assess transfer and efficiency are more appropriate.