In this work, we proposed a method for creating an Ag/Si composite structure consisting of an array of vertical silicon nanowires (SiNWs) decorated with silver nanoparticles (AgNPs). A two-stage metal-assisted chemical etching of Si was used to obtain the SiNW array, and atomic layer deposition was used to fabricate the AgNPs. A uniform distribution of AgNPs along the SiNW height was achieved. The measured characteristics by spectroscopic ellipsometry directly established the presence of AgNPs deposited on the SiNWs. The height of the sublayers and the fractions of Si and Ag in them were determined using the multilayer model and the effective Bruggeman medium approximation in the interpretation of the experimental data. For AgNP layers deposited on an Si wafer surface, the thickness (from 2.3 to 7.8 nm) and complex dielectric functions were verified within the framework of the Drude–Lorentz model. The optical properties of Ag/SiNW structures with complex spatial geometry were simulated in the COMSOL Multiphysics software. The expected localization of the electric field on the surface and near the AgNP was observed as a result of the plasmon resonance excitation. The calculated enhancement factor reached 10¹⁰, which indicates the possibility of using such structures as substrates for surface-enhanced Raman scattering.