Nowadays, multi-shelled mesoporous hollow metal oxide nanospheres have drawn a lot of attention due to their large internal space, nanometer scaled shell thickness, high specific surface area and well-defined mesopores, of which unique nanostructure endows metallic oxides with enhanced properties. In this thesis, we have studied and proposed a versatile ligand-assisted cooperative template method to synthesize multi-shelled mesoporous hollow metal hydroxides and oxides nanospheres, in which silica nanospheres act as sacrificial templates and the coordination interaction between metal ions and surfactant can be cooperatively amplified by using chelating ligand (ascorbic acid) as a co-template. The synthesized metal hydroxides and oxides nanospheres possess stable hollow structure, uniform spherical morphology and tunable diameter from 270 to 690 nm. All the multi-shelled mesoporous hollow metal hydroxide and metal oxide nanospheres exhibit high surface areas (up to 640 m²/g). The obtained Au nanoparticles loaded composited nanospheres exhibit excellent reactivity for solvent-free aerobic oxidation of ethylbenzene with high activity (28.2%) and selectivity (87%).