A large amount of fluorine−containing wastewater was produced with the rapid development of the industry. Excessive fluoride content in water will not only endanger ecological security but also pose threat to human health. In this study, common new adsorbents for defluorination, such as metal−based adsorbents, natural adsorbents, and nanomaterial adsorbents were reviewed for its physicochemical properties and fluorine removal efficiency. The fluorine removal mechanism of different adsorbents was introduced in detail, and the future work of the removal of fluorine using novel adsorbents was proposed. This research also introduces the application of the coupling of the adsorption method with the technology of chemical precipitation, filtration, and super−magnetic separation to treat high concentration of fluoride wastewater. A good selection of process combinations according to different needs can achieve high−efficiency defluorination in water. Finally, some existing problems of practical operation of fluorine using removal materials in the environment are summarized, hoping to contribute to the future research of fluorine removal materials.