This work focuses on the microwave-assisted hydrothermal synthesis of praseodymium-doped zirconia and on the subsequent evaluation of the effect of synthesis conditions on powder properties. Pure and 10 mol% Pr-doped zirconia samples have been analyzed by X-ray diffraction (XRD) and the perturbed angular correlations hyperfine technique, which probes the nearest environments of zirconium ions. At atomic scale, as determined from perturbed angular correlation data, the XRD amorphous fraction of the as-obtained powders exhibits a tetragonal-like structure. The pure powder becomes partially stabilized and the doped powder is a substitutional solid solution of praseodymium in tetragonal zirconia.