Environmental problems caused by heavy metal-containing wastewater pollution have seriously affected the functioning of the ecosystem and the production and life of human beings, and the solution of heavy metal (HM) water pollution has become an important issue. Meanwhile, due to the increasing shortage of HM resources, the effective extraction and recovery of valuable HM resources from industrial wastewater has also attracted extensive attention from researchers. The advantages of capacitive deionization (CDI) include high efficiency, being environmentally friendly, and low energy consumption. In recent years, CDI has been increasingly used in water treatment, and its research in HM separation and recovery has been increasing year by year. Considering that there is no comprehensive and in-depth review of this significant topic. Therefore, our review critically assesses the research progress of CDI in HM removal and recovery. We provide a brief introduction to HM and CDI, respectively, classify the mechanisms for selective separation of HM ions in CDI, summarize the relevant applications, analyze the existing problems, and anticipate their prospective future applications. Finally, the obstacles and potential of employing CDI for the selective separation and recovery of heavy metal ions are examined. The findings of this review will facilitate the advancement of CDI in HM separation and recovery and promote in-depth research on CDI in the field of ion-selective removal.