Using zirconium oxychloride hydrate ( ZrOCl2•8H2O) and ammonia water (NH3•H2O) as raw materials, and ammonium dihydrogen phosphate (NH4H2PO4) as additives, tetragonal zirconia (t-ZrO2) with size range of 8–12 nm were prepared by coprecipitation method under hydrothermal conditions. The influence factors on phase transformation and the particle size such as phosphor loading, hydrothermal temperature and calcination temperature were studied by X-ray diffraction (XRD), Fourier transform Roman spectra (FT-Roman), the Brunauer-Emmett-Teller (BET) method and X-ray photoelectron spectroscopy (XPS) techniques etc. Research results show that a small amount of phosphor has been incorporated into the framework of ZrO2 crystals, producing a certain amount of oxygen vacancies. Phosphor can effectively restrain crystal particles growth and improve the thermal stability of metastable t-ZrO2. The phosphor doped t-ZrO2 had a high surface area (244.2 m2/g). In contrast to the pure ZrO2 particles readily aggregating, the phosphor species deposited on the framework of ZrO2 crystals prevented the agglomeration of the primary particles during calcinations.