This work presents a surface-enhanced Raman scattering (SERS) and density functional theory (DFT) study of a fipronil adsorbed on colloidal silver nanoparticles (AgNPs). A standard curve was established to quantify fipronil within a range of 0.0001–0.1 ppm (r2 ≥ 0.985), relying on the unique fipronil Raman shift at ~2236 cm−1 adsorbed on AgNPs. DFT calculations suggest that the nitrile moiety (C≡N) binding should be slightly more favorable, by 1.92 kcal/mol, than those of the nitrogen atom of the pyrazole in fipronil and Ag6 atom clusters. The characteristic peaks of the SERS spectrum were identified, and both the calculated vibrational wavenumbers and the Raman intensity pattern were considered. The vibrational spectra of fipronil were obtained from the potential energy distribution (PED) analysis and selective Raman band enhancement.