Eu³⁺ doped luminescent nano–materials have become a research focus due to their outstanding physical and chemical properties in light–emitting, magnetism, thermology, catalysis and chemical activity etc.. Furthermore, the relationship between crystal structure and energy levels transition of these nano–materials can be easily obtained by measuring the spectra of doped Eu³⁺. Among luminescence nano–materials, ZrO₂ nano–crystal as a potential one has been attracted great attention in its higher refractive, good optical transparency and relatively low phonon energy. By now certain materials doped RE ion in the matrix ZrO₂ for ZrO₂∶Er³⁺–Y³⁺, ZrO₂∶Pr³⁺ and ZrO₂∶(Pr³⁺, Sm³⁺) etc., and mesoporous ZrO₂ nano–crystals doped Eu³⁺ by hydrothermal way have been reported. In present study, the ZrO₂∶Eu³⁺ nano–crystal was prepared with high purity and uniform composition by ion exchange method using strong OH⁻ as a precipitant. Its composition, morphology and structure were characterized by XRD, TEM, HRTEM and EDS. The experimental results show that it has a tetragonal crystal structure and its average grain size is 5—20 nm after calcined at 800 ℃ . It is found that the microstructure of ZrO₂∶Eu³⁺ changes slightly with the increase of calcining temperature till a small amount of monoclinic phase forms after calcined at higher than 900  ℃. The luminescent properteof Eu³⁺ in the ZrO₂ nano–crystal were measured by 3D emission and excitation spectra. The characteristic emissin bands of 590 nm (⁵D₀ →⁷F₁) and 606 nm (⁵D₀ →⁷F₂) of Eu³⁺ were observed at an excitation spectrum of λ_ex=394 nm. The luminescent properties of ZrO₂∶Eu ³⁺ are very sensitive to its microstructure change since slight changes in the ZrO₂∶Eu ³⁺ microstructure cause the changes in the shape and intensity of its emission spectra.