Abstract Here we report a methodology combining TEM, STEM, Transmission-EBSD and \{EELS\} to analyse the structural and chemical properties of the metal???oxide interface of corroded Zr alloys in unprecedented detail. TEM, \{STEM\} and diffraction results revealed the complexity of the distribution of suboxide grains at the metal???oxide interface. \{EELS\} provided accurate quantitative analysis of the oxygen concentration across the interface, identifying the existence of local regions of stoichiometric ZrO with varying thickness. Transmission-EBSD confirmed that the suboxide grains can be indexed with the hexagonal ZrO structure predicted with ab initio by Nicholls et al. (2014). The t-EBSD analysis has also allowed for the mapping of a relatively large region of the metal???oxide interface, revealing the location and size distribution of the suboxide grains.