Vanadium dioxide (VO₂) is a promising candidate for a solar heat controlling material that can be applied as an energy-efficient thermochromic smart window. However, drawbacks, such as chemical instability and low solar modulation of VO₂, have restricted its applications in this area. The synthesis of VO₂@shell is the easiest method for improving these properties. Herein, a novel moderately surfactant-free strategy is proposed for the synthesis of pure VO₂@SiO₂ core@shell nanoparticles to improve the optical and anti-oxidant properties of VO₂ particles, which involves potential interface chemistry for the synthesis of metal oxide@shell nanoparticles in a simple fashion. In addition, a MSNs/VO₂@SiO₂ composite film was designed, and this film exhibited better inoxidizability, higher luminous transmittance and a larger solar energy modulation ability than the pure VO₂ particles.