Capacitive deionization (CDI) is a promising technology for brackish water desalination because of its high efficiency, no secondary pollution and low cost. However, the ion removal capacity of CDI system for brackish water desalination is still insufficient. Herein, a new in-situ porous Cu template method is used to prepare a unique open three-dimensional mesoporous graphene foam (3DMG) with high CDI performance. The developed 3DMG material has rich mesoporous structure, interconnected pore structure, high specific surface area, good hydrophilicity and excellent electrical conductivity, which can achieve effective solution/pore contact, rapid ion migration and high electrosorption capacity. Therefore, the specific capacitance of 3DMG as high as 141.37F/g at 1 M NaCl and 10 mV/s, and the maximum salt adsorption capacity is as high as 32.08 mg/g (1000 mg/L, 1.2 V), which is significantly higher than that of graphene-based electrode materials reported in most literatures. It also shows excellent regeneration performance and stability after repeated electrosorption-desorption cycles. The developed 3DMG undoubtedly provides a promising electrode material platform for CDI devices, effectively solving the urgent problem of freshwater resource shortage.