Massive amount of highly contaminated mining residual materials (MRM) has been left unattended and has leached heavy metals, particularly lead (Pb) and zinc (Zn) to the surrounding environments. Thus, the performance of three immobilizers, raw dolomite (RD), calcined dolomite (CD), and magnesium oxide (MO), was evaluated using batch experiments to determine their ability to immobilize Pb and Zn, leached from MRM. The addition of immobilizers increased the leachate pH and decreased the amounts of dissolved Pb and Zn to different extents. The performance of immobilizers to immobilize Pb and Zn followed the following trend: MO > CD > RD. pH played an important role in immobilizing Pb and Zn. Dolomite in RD could slightly raise the pH of the MRM leachate. Therefore, the addition of RD immobilized Pb and Zn via adsorption and co-precipitation, and up to 10% of RD addition did not reduce the concentrations of Pb and Zn to be lower than the effluent standards in Zambia. In contrast, the presence of magnesia in CD and MO significantly contributed to the rise of leachate pH to the value where it was sufficient to precipitate hydroxides of Pb and Zn and decrease their leaching concentrations below the regulated values. Even though MO outperformed CD, by considering the local availability of RD to produce CD, CD could be a potential immobilizer to be implemented in Zambia.