To realize the solid materials with higher emission quantum yield from the rhodamine 6G (R6G) monomers, typical laser-dye, we hybridized both alkyltrimethylammonium (CnTMA+) and R6G cations into the laponite (Lap) interlayer nanospace and investigated their photoemission and nanostructure. The hybrid solid materials were prepared by dissolving an appropriate amount of CnTMA+Br− powder with Lap ethanol/aqueous (1/1 v/v) suspension with 0.1% or 0.5% cation-exchange capacity (CEC) of R6G cations. From X-ray diffraction (XRD) and 13C cross-polarization magic-angle spinning (CP MAS) NMR of the present solid materials, it was found that CnTMA+ cations were incorporated as the trans−gauche form into the Lap interlayer nanospace and R6G cations were intercalated parallel to the surface of Lap nanosheet. Emission quantum yield, ϕ, of the R6G/CnTMA+/Lap solid materials became higher than that of R6G/Lap and increased with increasing carbon number in alkyl chain, n, and was a constant as ca. 80% beyond n > 10. The R6G/C16TMA+/Lap solid material prepared under optimal conditions exhibited ca. 80% ϕ, even when the molar concentration of R6G cation was 10−2 mol/dm3.