A strategy for building ring-like deposit surface-enhanced Raman scattering (SERS) sensors with the coffee ring effect through the functional modification of the silica nanoparticle surface encapsulated by free-tagged Ag nanoparticles is addressed along with their applications in the SERS-based detection and degradation of target species, including paraquat, diquat, and their free radicals. The nanogap formed by two interparticles with SERS hotspots provides a gigantic amplification signal for the Raman scattering intensity of the analyte molecule located approximately at the hotspots. The enhanced Raman spectrum signals of these target analytes were achieved through the hotspot region of the surface plasmon resonance (SPR) located on the embankment formed by self-aggregation of SiO2@Ag nanoparticles due to the coffee ring effect. Meanwhile, the intrinsic properties of Ag nanoparticles embedded onto the silica surface were applied to photocatalytically degrade the target analytes by harvesting energy from sunlight. The SERS sensor detected the analytes down to 10–9 M in the aqueous solution.