Abstract: The ZnAl₂O₄: Mn photoluminescence nanocrystalline thin-film was grown on Si substrate. by using technique of spray pyrogenation. The result of the XRD analyses shows when content of the AlCl₃ in Zn（OH）₂ is more than 20% and the temperature of substrate is higher than 100℃, the ZnAl₂O₄-ZnO nanocrystalline compound film can be formed on the substrate. This film becomes the nanocrystalline film of spinel ZnAl₂O₄ after being processed by 0.1 mol/L hydrochloric acid. And the photoluminescence properties of the Mn²⁺ doped ZnAl₂O₄ nanocrystalline film were studied. The fluorescence spectrum shows a luminescent band in the 525 nm neighborhood, resulted from ⁴T₁（⁴G）-⁶A₁（⁶S） transition of the Mn²⁺ for this Mn²⁺doped ZnAl₂O₄ spinel nanocrystalline film.