We demonstrated for the first time that Ag-nanoparticle-decorated SiO2 nanospheres (NSs) may display noticeable photocatalytic activities upon surface plasmon resonance (SPR) excitation. The samples were prepared by reacting SiO2 NSs with AgNO3 in the seed-mediated growth process, from which the Ag particle size and decoration density can be readily controlled. The dependence of the SPR-mediated photocatalytic performance of Ag-decorated SiO2 NSs on the Ag morphology was investigated and presented. The as-prepared Ag-decorated SiO2 NSs showed a significantly red shifted and relatively broad SPR absorption when compared with the individually dispersed Ag nanoparticles. Owing to the considerably broad SPR absorption that spanned from the visible to the near-infrared region, Ag-decorated SiO2 NSs surpassed N-doped P-25 TiO2 powder and individually dispersed Ag nanoparticles in photocatalytic activity, demonstrating their potential as an active photocatalyst in nearly all the current photocatalysis applications. Furthermore, the result of performance evaluation under natural sunlight shows that the present Ag-decorated SiO2 NSs can be used as highly efficient photocatalysts that may practically harvest energy from sunlight. The current study provides a new paradigm for designing plasmonic metal nanostructures that can effectively absorb the entire solar spectrum and beyond for solar fuel generation.