Tris(8-hydroxyquinoline)aluminum (III) complexes (Alq3), one of the molecules studied most widely for organic light-emitting devices, were formed in the interlayer spaces of smectites by solid-solid reactions between Al-smectites (Al-montmorillonite and Al-synthetic saponite (Sumecton)) and 8-hydroxyquinoline (8Hq) at room temperature. The intercalation of 8-hydroxyquinoline molecules into Al-smectites was demonstrated by powder XRD, FTIR, DTA, TG, TG-MS, and chemical analysis. The coordination of the ligand to the interlayer Al cations was proved by FTIR, UV-Vis, and photoluminescence spectroscopies. The luminescence intensity of Alq3-Sumecton was much greater than that of Alq3-montmorillonite, and this was ascribed to the very small amount of quenching impurities in Sumecton.