Flower-shaped silver nanoparticles have been successfully synthesized by a simple aqueous phase silver nitrate reduction by ascorbic acid in the presence of polyvinylpyrrolidone (PVP) surfactant. The nanoparticles diameters were adjusted from 450 to 1000 nm with surface protrusions up to 10–25 nm. The growth direction of silver nuclei is controlled by their degree of coating by PVP. The flower-shaped silver nanostructures obtained were used as stable Surface Enhanced Raman Scattering (SERS) substrates with high SERS activity for detecting Rhodamine 6 G (R6 G), at a concentration of only 10−9 M, where the SERS signal is still clear. SERS spectra of the dye carmine was analysed and the characteristic bands were identified. An improved principle component analysis (PCA) was used for carmine detection, at concentrations down to 10−8 M. The characteristic peaks of the carmine (1019, 1360, and 1573 cm−1) remained at 10−8 M. This indicated that the minimum detection limit of AgNP-based substrate for carmine is about 10−8 M.