To reveal the properties of ZrO2 at the atom and electron levels, the valence elec- tron structures of three ZrO2 phases were analyzed on the basis of the empirical electron theory of solids and molecules. The results showed that the hybridization levels of Zr and O atoms in the m-ZrO2 were the same as those in the t-ZrO2, while those in the c-ZrO2 rose markedly. The electron numbers and bond energies on the strongest covalent bonds in the m-ZrO2 phase were the greatest, the values were 0.901106 and 157.5933 kJ/mol, respectively. Those in the t-ZrO2 phase took second place, which were 0.722182 and 123.9304 kJ/mol, and those in the c-ZrO2 phase were the smallest, which were 0.469323 and 79.0289 kJ/mol. According to the product of the bond energy on the strongest covalent bond and equivalent bond number (this value reflected the crystal cohesive energy), the order from the greatness to smallness was the c-ZrO2> t-ZrO2 > m-ZrO2. This showed that the m-phase bonds were the tightest, their energy was the smallest, the crystal cohe- sive energy of the m-phase was the largest, and the m-phase existed most stably at room temperature. So it must need energy or higher temperature to take apart the stronger covalent bonds to form a new phase. To reveal the properties of ZrO2 at the atom and electron levels, the valence electrons structures of three ZrO2 were were analyzed on the basis of the empirical electron theory of solids and molecules. The results showed that the hybridization levels of Zr and O atoms in the m-ZrO2 were the same as those in the t-ZrO2, while those in the c-ZrO2 rose markedly. The electron numbers and bond energies on the strongest covalent bonds in the m-ZrO2 phase were the greatest, the values ​​were 0.901106 and 157.5933 kJ / mol, respectively. Those in the t-ZrO2 phase took second place, which were 0.722182 and 123.9304 kJ / mol, and those in the c-ZrO2 phase were the smallest, which were 0.469323 and 79.0289 kJ / mol. According to the product of the bond energy on the strongest covalent bond and equivalent bond number (this value reflected the crystal cohesive energy), the order from the greatness to smallness was the c-ZrO2> t-ZrO2> m-ZrO2. This showed that the m-phase bonds were the tightest, their energy was the smallest, the crystal cohe- sive energy of the m-phase was the largest, and the m-phase successfully most stably at room temperature. So it must need energy or higher temperature to take apart the stronger covalent bonds to form a new phase.