Silica xerogels were prepared at different pH values in the range -0.8 to 1.2 and loaded with Rhodamin6G (Rh6G) dyes using the sol-gel technique and by variation of the HCl/TEOS and H₂O/TEOS ratios. The luminescence properties such as the spectral range of emission and the photostability of the laser dyes remain unchanged as a function of pH value at which the xerogels are prepared, although the porous structure of the xerogels is significantly changed. Inclusion of the dyes after gelation results in similar luminescence spectra as during-synthesis admixture of the dye. A detailed structural study using small angle X-ray scattering and nitrogen adsorption reveals that the dyes embedded by the postloading procedure occupy mainly micropores, while the dyes added during the sol-gel process are located mainly in mesopores. This is reflected in the position of the absorption maximum of the Rh6G dye, which is found at 506-516 nm for dyes in micropores and at 530-540 nm for dyes in mesopores.