Zirconia particles synthesized under ambient conditions are frequently amorphous, requiring heat to produce a crystalline phase. Synthesized nanoparticles are generally found in the tetragonal phase. In this article, a room temperature sol-gel synthesis of crystalline sub-10-nm zirconia particles is described. By adjusting the acid concentration of the reaction, it is found that the particles' crystalline phase can be modified. Under acidic conditions with moisture present, the tetragonal phase is produced, whereas under acidic conditions with low water content, 2-5-nm particles suggestive of the metastable orthorhombic phase are produced. Subsequent heat treatment of all powders produced with this technique resulted in their transformation first to the tetragonal phase, and ultimately to the monoclinic phase. The extent of the transformation to the monoclinic phase depends upon the atmosphere, however, suggesting that oxygen vacancies play a significant role in the stabilization and determination of the resulting phase.