The interface between hematite (α-Fe2IIIO3) and ilmenite (FeIITiO3), a weak ferrimagnet and an antiferromagnet, respectively, has been suggested to be strongly ferrimagnetic due to the formation of a mixed valence layer of Fe2+/Fe3+ (1:1 ratio) caused by compensation of charge mismatch at the chemically abrupt boundary. Here, we report for the first time direct experimental evidence for a chemically distinct layer emerging at heterointerfaces in the hematite—Ti-doped-hematite system. Using molecular beam epitaxy, we have grown thin films (~25 nm thickness) of α-Fe2O3 on α-Al2O3 (0001) substrates, which were capped with a ~25 nm thick Fe2−xTixO3 layer (x = 0.44). An additional 3 nm cap of α-Fe2O3 was deposited on top. The films were structurally characterized in situ with surface X-ray diffraction, which showed a partial low index orientation relationship between film and substrate in terms of the [0001] axis and revealed two predominant domains with \( (0001) _{{{\text{Fe}}_{2} {\text{O}}_{3} }} \;||\;(0001) _{{{\text{Al}}_{2} {\text{O}}_{3} }}, \) one with \( [10\bar{1}0]_{{{\text{Fe}}_{2} {\text{O}}_{3} }} \;||\;[10\bar{1}0]_{{{\text{Al}}_{2} {\text{O}}_{3} }}, \) and a twin domain with \( [01\bar{1}0]_{{{\text{Fe}}_{2} {\text{O}}_{3} }} \;||\;\;[10\bar{1}0]_{{{\text{Al}}_{2} {\text{O}}_{3} }}. \) Electron energy loss spectroscopy profiles across the Fe2−xTixO3/Fe2O3 interface show that Fe2+/Fe3+ ratios peak right at the interface. This strongly suggests the formation of a chemically distinct interface layer, which might also be magnetically distinct as indicated by the observed magnetic enhancement in the Fe2−xTixO3/α-Fe2O3/Al2O3 system compared to the pure α-Fe2O3/Al2O3 system.