Monodisperse polystyrene (PS) spheres with controllable size have been synthesized by a straight forward and simple procedure. The as-synthesized PS spheres have a typical diameter ranging from ~180 nm to ~900 nm, where a reduced sphere size is obtained by increasing the polyvinylpyrrolidone (PVP)/styrene weight ratio. The PS spheres function as sacrificial templates for the fabrication of hollow silica nanospheres (HSNSs) for thermal insulation applications. By modifying the silica coating process, HSNSs with different surface roughness are obtained. All resulting HSNSs show typically a thermal conductivity of about 20 mW/(mK), indicating that the surface phonon scattering is probably not significant in these HSNS samples.