In this Study, three chromophores-p-nitroaniline, 4-(4-nitrophenylazo)-aniline, and 4-[(E)-2-{4-[(E)-2-(4-nitrophenyl)-1-diazenyl]phenyl}-1-diazenyl] aniline-were intercalated into layered aluminosilicate saponite and then dispersed into the polyurethanes matrix. The intercalated chromophore/saponite complexes were examined by inductively coupled plasma emission and element analysis technologies. The molecular orbital package computation simulation and X-ray diffraction (XRD) analysis showed that possible configurations of chromophore ions on the gallery surfaces of saponite suggest that the chromophore molecules lie parallel to the basal planes of silicate as an inclined paraffin structure or as pseudo-multilayers. The XRD and transmission electron microscopy analysis indicated that the delamination of organoclay in the polyurethanes matrix exhibited nanolayers, exfoliated structure, or both. In particular, even at high doping levels up to 15 wt % of organoclay, the [chromophore](+)-saponite/polyurethanes film did not display a macroscopic aggregation of layered silicates and showed high transparency. The thermal stability of chromaphore was significantly enhanced as intercalated into the layered aluminosilicate saponite, and the glass-transition temperature of [chromophore](+)-saponite/polyurethanes nanocomposites proportionally increased with increased clay content.