The formation of silver nanostructures (AgNSs) with different crystals morphology in porous SiO2/p-Si templates by the electroless wet-chemical method at temperatures between 20 and 50 °C and surface-enhanced Raman scattering (SERS) was investigated. It was found that optimized dendritic silver architectures contain a significant number of localized “hot spots.” We show that well-reproducible AgNSs provide a significantly enhanced Raman signal of Nile blue dye molecules up to 10−6 M by using different excitation wavelengths (473, 532, and 633 nm). Based on our observations, the well-organized AgNSs can act as efficient surfaces for SERS as well as (bio)-sensor applications.