This study presents the intercalation into Layered Double Hydroxides (LDHs) of two sulfonated organic molecules featuring the mesoionic triazolium scaffold. These sulfonated fluorophores exhibited excellent solubility in aqueous basic solutions, facilitating their compatibility with the synthesis of LDHs through coprecipitation methods. We applied the size-matching interlayer space (SMIS) approach by substituting a portion of a mono- or dianionic surfactant used in LDH preparation by the sulfonated fluorophore, we aimed to match the size of the luminescent interleaved guest effectively. Our investigation focused on two anion spacers: the classic monoanionic dodecyl sulfate (DS) and the dianionic phenylene dipropionate (PPA). Our results indicated that the latter spacer allowed a more efficient insertion of the fluorescent guest. Thermal resistance analysis underscored the robustness of the final hybrid materials, suggesting a promising design strategy for luminescent materials when applied in diverse applications. Inorganic-organic hybrid materials obtained from mesoionic triazolium fluorophores and layered double hydroxides display highly efficient photoluminescence in the solid state.