Aiming at the design of new luminescent host-guest materials with minimized aggregation effects, two classes of sol-gel derived mesoporous materials were explored as hosts for Rhodamine 6G (Rh6G) dye: The first consists of pure (SiO2) and phenyl-modified silica (Ph0.17SiO1.915) xerogels, prepared via sol-gel reaction using an ionic liquid as catalytic agent. The second consists of mesoporous sodium aluminosilicate glasses with Si to Al ratio in the range of 6 ≤ Si/Al ≤ 9. Characterization through high resolution solid state NMR proved the successful obtention of the designed host matrices. Following Rh6G-loading in various concentrations, the resulting materials were characterized by their luminescence and excitation spectra, excited state lifetimes, and quantum yields. The dye doped silica xerogels presented high quantum yield values (up to 87%), with no substantial decrease in efficiency with increasing dye concentration. At suitable Rh6G contents, all the final materials presented laser action under 532 nm excitation from a Q-switched frequency doubled Nd:YAG laser. The phenyl silicate sample presents the highest laser photostability with a half-life of 6560 pulses, under 2 mJ/pulse pump power, and 10 Hz repetition rate. The laser experiments provided further insights on the photodegradation mechanisms of such organic species.