In the case of a hypothetical loss of primary coolant accident (LOCA) in a light water reactor, the zirconium alloys fuel cladding would be oxidized in steam at high temperature, typically in the range 800–1200 °C. The monoclinic to tetragonal phase martensitic transition of zirconia occurs within this temperature range and complex phenomena possibly having an impact on the oxidation kinetics are then to be expected. In order to provide an accurate description of the structure and microstructure of the oxide layers, systematic X-ray diffraction analyses have been performed in-situ under oxidizing atmosphere at high temperature (between 800 and 1100 °C) on Zircaloy-4 and M5™ sheet samples. It was confirmed that the volume fraction of the tetragonal and monoclinic zirconia phases formed during oxide growth drastically depends on the oxidation temperature. For example, the few outer microns of the oxide are fully tetragonal above 1050 °C and contain only 20% of tetragonal phase at 800 °C. It was also shown that cooling after oxidation induces irreversible phase transitions within the oxide. As a consequence, both the structure and the microstructure of the growing oxide cannot be observed post-facto, neither at room temperature nor after reheating at the prior oxidation temperature. It has been deduced from microstructural analyses that the grain size of the tetragonal zirconia phase is nanometric, about 100 nm during oxidation at 1100 °C down to 20 nm after cooling down to room temperature. This small grain size allows the stabilization of the tetragonal phase. The lattice parameters of the monoclinic and tetragonal zirconia phases have been analyzed, during both high temperature oxidation and cooling. In both cases, it appears the ‘a’ and ‘b’ cell parameters of the monoclinic phase are strongly constrained by the tetragonal ‘a’ one. The structural characteristics of the oxide formed at high temperature on Zircaloy-4 and M5™ are quite similar. All those results can be interpreted in the frame of the classical description of the monoclinic–tetragonal martensitic transition of zirconia.