The development of hybrid materials with unique optical properties has been a challenge for the creation of high-performance composites. The improved photophysical and photochemical properties observed when fluorophores interact with clay minerals, as well as the accessibility and easy handling of such natural materials, make these nanocomposites attractive for designing novel optical hybrid materials. Here, we present a method of promoting this interaction by conjugating dyes with chitosan. The fluorescent properties of conjugated dye–montmorillonite (MMT) hybrids were similar to those of free dye–MMT hybrids. Moreover, we analyzed the relationship between the changes in optical properties of the dye interacting with clay and its structure and defined the physical and chemical mechanisms that take place upon dye–MMT interactions leading to the optical changes. Conjugation to chitosan additionally ensures stable adsorption on clay nanoplatelets due to the strong electrostatic interaction between chitosan and clay. This work thus provides a method to facilitate the design of solid-state hybrid nanomaterials relevant for potential applications in bioimaging, sensing and optical purposes.