Structural variations and phase stability in 3 mol% yttria stabilized tetragonal zirconia (3Y-TZP) subjected to long-term aging at room temperature and thermal treatments in air were investigated by Raman and X-ray photoelectron spectroscopies, and compared with previous cases obtained by hydrothermal treatments. The results revealed a significant difference in the kinetics of zirconia polymorphic transformation in different environments due to the critical roles played by surface and lattice hydroxyl defects. Thermal treatments in air of long-term stored 3Y-TZP revealed a gradual recovery to tetragonal phase due to the ocurrence of dehydroxylation, while thermal treatments of pristine 3Y-TZP caused tetragonal-to-monoclinic polymorphic transformation at low temperature, but then an inverse transformation at higher tempertures due to a competition of hydroxylation and dehydroxylation. Treatments of 3Y-TZP in different environments were found to lead to distinct paths of off-stoichiometric chemistry, including hydroxylation, hydroxyl migration, surface reconstruction, and dehydroxylation during the treatments.