Silicon nanowires (SiNWs) were comprehensively characterized in dependence on conditions of their formation via metal (Ag) -assisted chemical etching (MACE) of monocrystalline Si. The Ag structures remained on/between SiNWs based on both n- and p-Si were found to promote surface enhancement of Raman scattering (SERS) from organic molecules adsorbed on their surface. The Ag structures on/between the SiNWs/p-Si facilitated two times higher SERS-signal from 10-6 M rhodamine 6G than those in the SiNWs/n-Si. The activity of the SERS-substrates based on p-Si was improved by modification with small Au dendrites, which provided rich family of hot spots and prevented degradation of the SERS-activity observed for pure Ag dendrites due to formation of Ag2S during one week of storage in air. The SERS-substrates based on the Au/Ag dendrites on SiNWs/p-Si allowed to achieve nanomolar detection limit of rhodamine 6G and 5,5′-dithiobis (2-nitrobenzoic acid).