Eu3+-doped zirconia nanopowders were prepared by the sol-gel technique using two different methods, based on the hydrolysis of zirconium n-propoxide, producing tetragonal and monoclinic zirconia under different preparation conditions. A detailed microstructure characterization was performed through wide angle x-ray scattering, small angle x-ray scattering, trasmission electron microscopy, and nitrogen physisorption measurements. The possible influence of the zirconia crystalline phases and particle sizes on the luminescence properties of the lanthanide ion was investigated. A detailed analysis of the emission spectra of the samples suggested that the dopant Eu3+ ions replace the Zr4+ ions in the zirconia crystal lattice. Moreover, samples prepared by the two different methods were characterized by different decay times of the Eu3+ ion luminescence.