A silica and polyvinyl alcohol (PVA) hybrid material mixed with a high density of silver ions is synthesised and characterized in this work. The hybrid material can be cast into thick films, which we determined to be homogeneous using Raman spectroscopy. We observed that the silver ions remain stable in the material over time and at temperatures of 100 °C, which represents a marked improvement over previous solid solutions of silver. Differential scanning calorimetry and thermogravimetric analysis indicate the rapid activation of silver at 173 °C, resulting in a dense formation of silver nanoparticles within the hybrid. The activation of silver was also demonstrated in 3-dimensional geometries using femtosecond duration laser pulses. These results illustrate the silica-PVA hybrid is an attractive material for developing silver-insulator composites.