Design and preparation of various rational silver micro-nanostructures has been recognized as a promising solution for the Surface-enhanced Raman scattering (SERS) signal amplification. Here, a simple wet-chemical method was reported for the synthesis of high-density Ag dendrites structures on silicon wafer by rapidly mixing silver nitrate and hydrofluoric acid aqueous solutions. The reductive Si-H surfaces is oxidized while silver ions are reduced, yielding a final Ag dendrites structure that offers an excellent SERS enhancement. The EDS measurements confirmed the metallic nature of the formed Ag dendrites. Researches also show that the pure and low-cost Ag dendrites were about several micrometers in size and can be rapidly and reproducibly produced in high yield. Importantly, there were no organic contaminants were detected on the surface of the resulting dendrites structure. Additionally, the influence of experimental parameters on the morphology of dendrites was also been investigated, such as hydrofluoric acid concentration, silver nitrate concentration, and the reaction time. Importantly, the fabricated Ag dendrites substrates can be used for accurate and reliable determination of Sudan I, Sudan II, and Sudan III, which indicate that they could have a good future for implementation.