Precise control of the size, composition, and assembly process of each component is expected to play a key role in the construction of integrated functional nanostructures. Herein we report a unique sacrificial template method for the fabrication of noble metal@silica hollow microspheres with noble metal (Au, Pt, and Pd) nanoparticles uniformly immobilized on the inner surfaces of silica hollow microspheres. A polystyrene microsphere as a sacrificial template is used to play dual roles, creating a cavity inside the silica microsphere and introducing noble metal nanoparticles into the silica microsphere. Distinct from the reported sacrificial template methods, this method takes advantage of a thermodynamic effect to easily deposit the noble metal nanoparticles with different sizes and compositions onto the template microspheres. In addition, taking Au@silica hollow microspheres for example, they exhibit excellent catalytic activity and recyclability for the reduction of p-nitrophenol (4-NP) by NaBH4.