The removal of Cd, Cu, Ni and Zn from dilute mine water by using several geological materials including pure limestone, sand, carbonaceous limestone and brecciated limestone was performed on a laboratory scale. The results showed that to add geological materials in combination with sodium carbonate injection would notably enhance the efficiency of heavy metal removal to varying degrees. Pure limestone was found the best one among the four materials mentioned above for removing heavy metals from mine water. The removal efficiencies of pure limestone when it is ground as fine as 30-60 meshes are 58.6% for Cd, 100% for Cu, 47.8% for Ni, and 36.8% for Zn at 20℃. The optimum pH is about 8.9 to 9.1. The mechanism of higher effective removal, perhaps, is primarily due to co-precipitation under the control of calcite-related pH value. According to this research, Na2CO3 injection manners, including slug dosing and drip-wise, seemed to have little impact on the efficiency of heavy metal removal.