Absorption and fluorescence spectroscopies with linearly polarized light are applied to characterize the adsorbed species of rhodamine 6G (R6G) laser dye in ordered organophilic laponite (Lap) clay films for low dye loadings. The organophilic character of the clay was controlled by the number of organic surfactant dodecyl-trimethylammonium (C12TMA) cations intercalated into the interlayer space of the clay. Experimental results suggest that for moderate to high surfactant contents (>70% of the total cation exchange capacity, CEC, of the clay) the accessibility of the interlayer space for R6G molecules is reduced. In these cases, the first stage in the adsorption of R6G molecules is at the external surface, where dye molecules can self-associate even for very low dye loading (around 0.1%CEC), probably for the limitation of the external surface area. The presence of a nonfluorescent H-type aggregate with a short-displaced coplanar structure and a fluorescent oblique head-to-tail J aggregate is reported. The inclined structure of this J aggregate is stabilized by the surfactant molecules at the external surface.