Sensing technologies based on metallic nanoparticles, known as Ag, Au, and so on, have raised enormous interest for their extraordinary sensing resolution and sensitivity to analytes of chemical or biological importance under optical detection have received wide attention in recent decades. Currently, a discrete nanoparticle in a free-standing form, either being organically or biologically modified on the nanoparticle surface, on a given substrate surface region has been employed for photosensing purpose. However, metallic nanoparticles suffering from physical and chemical instability such as oxidation, interparticle coupling, agglomeration, and so on during the processing stages may render undesirable outcomes, which further results in poorer performance than the theoretical expectation. Here we propose a facile and elegant concept to prepare an Ag-decorated silica nanoparticle (hereinafter termed core-shell SiO2@Ag nanosphere) based on the modified Stöber method. The Ag nanoparticles with an average size controlled at about 1, 3, and 5 nm deposited over the surface of the silica nanocarrier were well separated, making the resulting SiO2@Ag nanospheres. The nanospheres showed physically and optically stable surface plasmon resonance spectra and also demonstrated a relatively high Ag-sized dependent sensitivity to ppb level for the detection of analyte molecule, that is, melamine. Theoretical model fitting has been well managed to correlate the optical behavior of the nanosensors, and the outcomes strongly indicated a promising potential of the Ag-decorated SiO2 core-shell nanospheres for sensory applications.