Integrating hollow silica spheres with metal nanoparticles to fabricate multifunctional hybrid materials has attracted increasing attention in catalysis, detection, and drug delivery. Here, we report a simple and general method to prepare hollow silica spheres encapsulating silver nanoparticles (Ag@SiO2) based on spherical polyelectrolyte brushes (SPB), which consist of a polystyrene core and densely grafted poly (acrylic acid) (PAA) chains. SPB were firstly used as nanoreactors to generate silver nanoparticles in situ and then used as sacrificial templates to prepare hybrid hollow silica spheres. The resulted Ag@SiO2 composites exhibit high catalytic activity and good reusability for the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. More importantly, this developed approach can be extended to the encapsulation of other metal nanoparticles such as gold nanoparticles into the hollow silica spheres. This work demonstrates that SPB are promising candidates for the preparation of hollow spheres with encapsulated metal nanoparticles and the resulted hybrid spheres show great potential applications in catalysis.