Rare earth ions Sm3+ doped monoclinic and tetragonal zirconia have been prepared by solid state synthesis (SS) and combustion (CB) respectively. The crystallization, phase transformation, and luminescence properties of Sm3+ are controllable through synthesis procedure, reaction temperature and the concentration of rare earth ion dopants. The morphologies of ZrO2 nanoparticles have been studied by TEM and HTEM. Beside XRD, the photoluminescence spectra provide another efficient way to probe the structure of zirconia as the luminescence properties of rare earth ions activators are sensitive to the surrounded environment in different structured zirconia.