An organo-montmorillonite (MMT) complex [poly-diallyldimethyl(PDDA)-Kunipia F] with various loadings of polycation was modified with a laser dye Rhodamine 6G (R6G) to obtain a photofunctional hybrid materials for monitoring of dye-polymer-MMT nanocomposite interactions. The polymer-MMTs were prepared in a colloidal state via ion-exchange reaction. The content of polycation (PDDA) in suspensions varied from 20 mg to 1000 mg per 1 g of Kunipia F (KF) MMT. Dramatic changes was observed in the structure of PPDA-MMT containing 200-300 mg of polymer per 1 g of KF, which was the saturation point of the polycation for this system. The PDDA molecules were able to suppress the formation of nonluminescent H-aggregates and to enhance the overall luminescence properties. The PDDA/MMT nanocomposite systems are the novel ones that have not been studied before in order to prepare highly fluorescence hybrid systems. (c) 2013 Wiley Periodicals, Inc.