Heavy metal pollution treatment in industrial wastewater is crucial for protecting biological and environmental safety. However, the highly efficient and selective removal of heavy metal ions from multiple cations in wastewater is a significant challenge. This work proposed a pulse electrochemical method with a low-/high-voltage periodic appearance to selectively recover heavy metal ions from complex wastewater. It exhibited a higher recovery efficiency for heavy metal ions (100% for Pb 2+ and Cd 2+ , >98% for Mn 2+ ) than other alkali and alkaline earth metal ions (Na + , Ca 2+ , and Mg 2+ were kept below 3.6, 1.3, and 2.6%, respectively) in the multicomponent solution. The energy consumption was only 34-77% of that of the direct current electrodeposition method. The results of characterization and experiment unveil the mechanism that the low-/high-voltage periodic appearance can significantly suppress the water-splitting reaction and break the mass-transfer limitation between heavy metal ions and electrodes. In addition, the plant study demonstrates the feasibility of treated wastewater for agricultural use, further proving the high sustainability of the method. Therefore, it provides new insights into the selective recovery of heavy metals from industrial wastewater.