In this paper, we present a simple method to synthesize eccentric Au@SiO2 Janus nanoparticles. By simply tuning the concentration of poly(vinyl pyrrolidone) (PVP), the surface of gold nanoparticle can be partially or fully wrapped with the amphiphilic ligand. As a result, Janus nanoparticle or concentric core-shell nanostructures can be obtained, respectively. A systematic study has been carried out to confirm the function of PVP molecules. The as-prepared Janus nanoparticle can act as a catalyst to catalyze the reduction of 4-nitrophenol, while the core-shell nanostructure is not active due to the coverage of dense silica shell. This work provides a robust and scalable method to produce Au@SiO2 Janus nanoparticles.