The design and synthesis of hollow/yolk-shell mesoporous structures with catalytically active ordered mesoporous shells can infuse new vitality into the applications of these attractive structures. In this study, we report that hollow/yolk-shell structures with catalytically active ordered mesoporous aluminosilica shells can be easily prepared by using silica spheres as the silica precursors. By simply treating with a hot alkaline solution in the presence of sodium aluminate (NaAlO(2)) and cetyltrimethylammonium bromide (CTAB), solid silica spheres can be directly converted into high-quality hollow mesoporous aluminosilica spheres with perpendicular pore channels. On the basis of the proposed formation mechanism of etching followed by co-assembly, the synthesis strategy developed in this work can be extended as a general strategy to prepare ordered mesoporous yolk-shell structures with diverse compositions and morphologies simply by replacing solid silica spheres with silica-coated nanocomposites. The reduction of 4-nitrophenol with yolk-shell structured Au@ordered mesoporous aluminosilica as the catalyst has clearly demonstrated that the highly permeable perpendicular pore channels of mesoporous aluminosilica can effectively prevent the catalytically active yolk from aggregating. Furthermore, with accessible acidity, the yolk-shell structured ordered mesoporous aluminosilica spheres containing Pd yolk exhibit high catalytic activity and recyclability in a one-pot two-step synthesis involving an acid catalysis and subsequent catalytic hydrogenation for desired benzimidazole derivative, which makes the proposed hollow ordered aluminosilica spheres a versatile and practicable scaffold for advanced catalytic nanoreactor systems.