Metastable tetragonal zirconia nanocrystallites were studied in humid air and in water at room temperature (RT). A stabilizing effect of different surfactants on the tetragonal phase was observed. Furthermore, the phase stability of silanized metastable tetragonal zirconia nanocrystallites was tested by prolonged boiling in water. The samples were analyzed with X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Changes in the monoclinic volume fraction in the samples were calculated. A number of surfactants were screened for their ability to stabilize the tetragonal phase upon exposure to humidity. Only silanes and phosphate esters of these were able to stabilize the tetragonal phase in water. Even as small amounts of silanes as 0.25 silane molecule per nm(2) are able to stabilize the tetragonal phase in water at RT. Aminopropyl trimethoxy silane and gamma-methacryloxypropyl trimethoxy silane were even capable of preventing phase transformation during boiling for 48 h in water.