Thin solid films of well-crystallized layered double hydroxides (LDHs) containing anionic fluorescein dye (AFD) and 1-butanesulfonate (C_4S) were prepared. Well-crystallized LDH thin solid films were first synthesized by immersing glass substrates into a nitrate-type LDH aqueous suspension prepared using a hydrothermal method. The LDH/AFD/C_4S hybrid thin solid films were then prepared by immersing the well-crystallized LDH thin solid films in aqueous solutions of AFD and C4S. Notably, the level of AFD hybridization was readily controlled by varying the concentration of the AFD in the aqueous solution (the C4S concentration was held constant at 800 or 2000% of the anion exchangeable sites in the LDH). The prepared LDH/AFD/C_4S hybrid thin solid films exhibited remarkable photoluminescence properties under UV light irradiation that responded to changes in humidity.