To clarify the structure and species of rhodamine 6G (R6G) aggregates formed in taeniolite (TN) interlayer spaces, the oriented thin films of R6G-TN hybrid materials were prepared and analyzed. XRD investigations of these films indicated that the R6G molecules were intercalated in the TN interlayers and that the TN layers were parallel to the glass plate in the thin films. Most of the intercalated R6G molecules were assumed to form various kinds of H-type aggregates in the TN interlayer spaces, since the R6G-TN hybrid films exhibited no emission spectrum by excitation at lambda = 530 nm. The peak-deconvolution results of the UV/vis absorption spectra of the hybrid films indicated that there was one kind of H-type R6G dimer in the thin film. Moreover, polarized UV/vis spectroscopy revealed the existence of high-order aggregates in addition to these dimers. The high-order aggregates, but not the dimers, were found to be aligned perpendicularly to the TN surface in the TN interlayer spaces.