AbstractDopant segregation, frequently observed in ionic oxides, is useful for engineering materials and devices. However, due to the poor driving force for ion migration and/or the presence of substantial grain boundaries, dopants are mostly confined within a nanoscale region. Herein, we demonstrate that core–shell heterostructures are formed by oriented self-segregation using one-step thermal annealing of metal-doped hematite mesocrystals at relatively low temperatures in air. The sintering of highly ordered interfaces between the nanocrystal subunits inside the mesocrystal eliminates grain boundaries, leaving numerous oxygen vacancies in the bulk. This results in the efficient segregation of dopants (~90%) on the external surface, which forms their oxide overlayers. The optimized photoanode based on hematite mesocrystals with oxide overlayers containing Sn and Ti dopants realises high activity (~0.8 μmol min⁻¹ cm⁻²) and selectivity (~90%) for photoelectrochemical H₂O₂ production, which provides a wide range of application for the proposed concept.