We demonstrate a new technique to fabricate silver dendritic structures in a subsurface glass layer based on electrolysis of silver-enriched glass. Chemical etching of glass in water diluted HF allows “opening” of the dendrites for their characterization, which makes possible their use for Surface-enhanced Raman scattering. The structure and morphology of the dendrites were characterized using atomic force and scanning electron microscopy, and energy-dispersive X-ray spectroscopy. It was demonstrated that the surface morphology of the formed structures depends on the electric charge passed through the sample during the electrolysis and the duration of the chemical etching. The presented method does not require expensive equipment and materials and allows one to form silver nanostructures of a prescribed pattern.