Interactions between smectite clay minerals and various organic dyes have been studied extensively, but little information has accumulated from dye interactions with mixed-layer illite-smectite (I-S) minerals, especially regarding relationships with clay layer expandability, layer charge, particle size/ shape, and molecular aggregation of organic dye molecules. The purpose of this study was to investigate the surface interactions of a set of mixed-layer illite-smectites from different geological environments with Rhodamine 6G dye. The samples used have different amounts of expandable smectite interlayers, different particle size and/or shape, and different layer-charge density at the surface. Five smectites with differences in layer charge and some non-expandable layer silicates were also tested. The interactions detected by UV-vis spectroscopy show no reaction between R6G and non-expandable minerals (kaolinite, mica), and intense reactions forming H-aggregates and monomers with smectites and illite-smectites. The intensity of H-aggregate formation increases with increase in the layer charge of smectites. Mixed-layer illite-smectites interact with R6G more intensely than do smectites. H-aggregate and monomer formation increases with the illitization process for randomly ordered illite-smectites (R = 0) and decreases in the course of illitization for the ordered illite-smectites (R > 0).