The layers of a Zn/Al layered double hydroxide (LDH) were doped with Dy³⁺cations. Among some compositions, the Zn²⁺ : Al³⁺ : Dy³⁺molar ratio equal to 30 : 9 : 1 presented a single crystalline phase. Organic anions with carboxylic, amino, sulfate, or phosphate functional groups were intercalated as single layers between LDH layers as confirmed by X-ray diffraction and infrared spectroscopy. Photoluminescence spectra of the nitrate intercalated LDH showed a wide emission band with strong intensity in the yellow region (around 574 nm), originated due to symmetry distortion of the octahedral coordination in dysprosium centers. Moreover, a broad red band emission was also detected apparently due to the presence of zinc oxide. The distorted symmetry of the dysprosium coordination environment, also confirmed by X-ray photoelectron spectroscopy analysis, was modified after the intercalation with phenyl phosphonate (PP), aspartate (Asp), adipate (Adip), and serinate (Ser) anions; the emission as measured from PL spectra of these LDH was more intense in the blue region (ca. 486 nm), thus indicating an increase in symmetry of dysprosium octahedrons. The red emission band from zinc oxide kept the same intensity after intercalation of dodecyl sulfate (DDS). An additional emission of unknown origin atλ= 767 nm was present in all LDHs.