Nonagglomerated spherical ZrO2 particles of 5–8 nm size were made by emulsion precipitation. Their crystallization and film-forming characteristics were investigated and compared with nanosized ZrO2 powders obtained by sol–gel precipitation. High-temperature X-ray diffraction indicated that the emulsion-derived particles are amorphous and crystallize at 500°C into tetragonal zirconia, which is stable up to 1000°C. Crystallite growth from 5–20 nm occurred between 500°–900°C. Films of 6–75 nm thickness were made by spreading, spin coating, and controlled deposition techniques and annealed at 500°–600°C. The occurrence of t-ZrO2 in the emulsion-precipitated powder is explained by the low degree of agglomeration and the corresponding low coarsening on heating to 500°–800°C, whereas the agglomerated state of the sol–gel precipitate powder favors the occurrence of the monoclinic form of zirconia under similar conditions.