Metal oxides are the basis of a vast range of technologies and are typically subject to defect engineering to cater for demands across multiple different applications. For instance, incorporation of Sn or Mg into In2O3 leads to n-or p-type conductivity ; introducing rare earth elements brings about light emission ; doping with transition metals like Fe, Co, Cr and Ni gives rise to dilute magnetic semiconductors . Among others, native point defects play a particularly important role in metal oxides. Compared with extrinsic impurities, native defects are ubiquitously present and exert a significant influence on material properties. For instance, O vacancy (Vo), the most stable native defect in many oxides, is found to play a key role in conductivity , light-emission , photocatalysis, magnetism and gas sensing. Therefore, understanding and controlling native defects is essential for metal oxides.