Melt of NaCO3 can favor oxidation of Zr to form ZrO2 thin film on Zr surface, which is used to make Zr/ZrO2 oxidation/reduction electrode of pH sensor for testing elevated temperature aqueous solutions. Using SEM, EPMA, XPS, EXAFS and HRTEM, we found that ZrO2 film is tightness and solid with 20 mu m thickness composed by nanometer-sized monoclinic crystals. Zr/ZrO2 interface is characterized of zoning structure according to topography and chemical composition in five zones: oxygen-rich ZrO2, ZrO2, oxygen-rich Zr metal, oxygen-bearing Zr and Zr from outmost to center. Melt oxidation process of Zr involved oxidation time, air and temperature. The air is important effect on structural and electrochemical properties of ZrO2 thin film for making elevate temperature electrochemical sensor. If oxygen air largely presented in carbonate melting process, ZrO2 thin film is not tightness and not for oxidation/reduction electrode.