ZrO 2 :Eu 31 hollow spheres were successfully fabricated with the resin microspheres as the template. The sample characterizations were carried out by means of x-ray diffraction (XRD), scanning electron microscope (SEM), and photoluminescence spectra. XRD results revealed that Eu 31 -doped samples were pure t-ZrO 2 phase after being calcined at 873 K. SEM results exhibited that this Eu 31 doped ZrO 2 was hollow spheres; the diameter and thickness of which were about 450 and 50 nm, respectively. Upon excitation at 394 nm, the orange-red emission bands at the wave length longer than 570 nm were from 5 D 0 ! 7 F J (J 5 1, 2) transitions. The asymmetry ratio of ( 5 D 0 ! 7 F 2 )/( 5 D 0 ! 7 F 1 ) intensity is about 1.61, 1.26, 1.42, 1.42, 1.40, and 1.38 for the Eu 31 concentration 0.4, 0.7, 1.0, 1.5, 2.0, and 2.5 mol%, respectively. These values suggest that the asymmetry ratio of Eu 31 ions is independent of the doping concentration. The optimal doping concentration of Eu 31 ions in ZrO 2 is 1.5 mol%. According to Dexter's theory, the critical distance between Eu 31 ions for energy transfer was determined to be 16 Å.