Layered double hydroxides (LDHs) are a class of anionic clay materials. When calcined at a certain temperature range, LDHs decompose into corresponding mixed metal oxides (Ox), which are regarded as promising electrode materials for capacitive deionization (CDI). We have developed a simple yet efficient strategy for in situ assembly of the MgAl-Ox nanosheets on graphene (G). The as-obtained MgAl-Ox/G nanohybrids with numerous channels for the access of anion exhibited high surface area and high electrical conductivity. When used as the anode of CDI cell, MgAl-Ox/ G nanohybrids exhibited excellent cycling stability and high electrosorption capacity due to its the memory effect and oxidation resistant property.