By combining high-resolution transmission electron microscopy and scanning transmission electron microscopy with analytical capability, we investigated the nanostructure of a textured hematite photoanode with columnar grains obtained by the colloidal deposition of magnetite nanocrystals. This initial report describes in detail the structure and chemistry of the α-Fe2O3/SnO2:F interface by identifying semicoherent and incoherent interfaces as well as a localized interdiffusion layer of Sn and Fe at the interface (∼100 nm in length). Our study indicates that unintentional doping by tin at a high sintering temperature is not significant in enhancing hematite photoanode performance for water oxidation. The correlation of nanoscale morphology with photoelectrochemical characterization facilitated the identification of the beneficial effect of a preferential growth direction of a hematite film along the [110] axis for water-splitting efficiency.