ZrO(2)-10, 12 and 14 mol% Sc(2)O(3) nanopowders were prepared by using a nitrate-lysine gel-combustion synthesis. These materials were studied by synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy after calcination at different temperatures from 650 to 1200 degrees C, which led to samples with different average crystallite sizes, up to about 100 nm. The results from SXPD and Raman analyses indicate that, depending on Sc(2)O(3) content, the metastable t''-form of the tetragonal phase or the cubic phase are fully retained at room temperature in nanocrystalline powders, provided an average crystallite sizes lower than approximately 30 nm. By contrast, powders with larger average crystallite sizes exhibit the stable rhombohedral, beta and gamma, phases and do not retain or very partially retain the metastable t'' and cubic ones.