A facile method for the synthesis of a series of mesoporous silica nanoporous (MSN) aqueous miscible organic layered double hydroxide core@shell nanocomposites using MCM-41, Al-MCM-41, SBA-15, and MCM-48 as the core is reported. These materials exhibit hierarchical morphologies with high surface areas and good porosity. Chemically, these materials offer controllable bifunctional basicity and acidity.