Abstract The optical properties of rhodamine 6G dye confined in porous silica are reported. Photoluminescence properties of embedded chromophores in mesoporous hosts can be affected by the surrounding matrices: shifts in emission spectra and variations of photoluminescence quantum yield are found as compared to dye solutions. Host–guest interactions are studied here by varying both SiO2 xerogels porosity and the dye concentration. Comparing samples obtained by impregnating matrices with 5.4 and 18.2 nm pores with solutions having concentrations in the rhodamine 6G high laser gain, matrices with 5.4 nm pores impregnated with a dye concentration of 5 × 10− 4 M are found to be the most stable and efficient in the examined range.