The role of the material structure in the energy transfer between Ag and Tb³⁺/Yb³⁺ ions is studied in silica-soda-zirconia sol-gel glasses and glass-ceramics. The preparation of Tb³⁺ and Yb³⁺ doped silica-soda-zirconia layers was carried out by sol-gel and dip-coating, followed by thermal annealing. The precipitation of zirconia nanocrystals was obtained by controlling the annealing temperature: from a full amorphous glass at 700 °C into a glass-ceramic at 1000 °C. A different crystalline structure of zirconia nanocrystals, tetragonal or cubic, was controlled by the rare-earth doping and investigated in relation to the Tb3+/Yb3+ optical properties. Moreover, Ag codoping was introduced by ion-exchange, obtaining a significant photoluminescence enhancement, both in the intensity and in the broadness of the excitation band, covering the whole UV region and part of the violet-blue region. Ag-sensitized Tb³⁺/Yb³⁺ doped silica-soda-zirconia glass-ceramics were attested to be potential candidates for energy-related applications, such as spectral conversion layers for solar cells, lasers and light-emitting devices (LEDs) in the visible and NIR spectral regions.