Currently, chloride ions in industrial water limits its reuse when extending the circulating water cycle. Therefore, it is necessary to remove Cl− to ensure its effective reuse. Considering the development of new materials for efficient electrochemical chloride removal is a key issue limiting the development of capacitive deionization technology for chlorine removal. In this study, BiOCl was grown in situ on the surface of V-MXene, and then a nanoflower-like BiOCl/MXene composite was synthesized by utilizing the properties of MXene as a structure-directing agent to modulate the morphology, which exhibits superior pore structure and specific capacitance. The poly (diallyl dimethylammonium) (PDDA) modification improved the materials’ specific capacitance and reduced energy consumption for dichlorination. The optimal BMP-10 exhibited superior performance for dichlorination, the maximum dichlorination capacity and rate were 161.64 mg g−1 and 2.20 mg g−1 min−1. We found that MXene has excellent properties for exfoliation and morphology modulation of layered materials. Additionally, the electrical properties have an important influence on the electrochemical removal of chloride ions. Here we successfully synthesized an efficient electrode material with unique morphological structure for CDI dichlorination and provided ideas for structure-directing agents and electrical modulation in material design for electrochemical dichlorination.