AbstractIlmenites from the least-altered rocks of the Beja-Acebuches Ophiolite Complex (SE Portugal), with low Ti values and excess Fe, despite rare optical evidence of hematite exsolution, were studied by ⁵⁷Fe Mössbauer spectroscopy and X-ray diffraction. According to single-crystal XRD the sequence of alternate layers characteristic of the ideal ilmenite structure is preserved, the excess Fe being accommodated in the Ti layers. No superparamagnetic oxides were detected by ⁵⁷Fe Mössbauer spectroscopy. The typical spectra of bulk αFe₂O₃ and of Fe³⁺-containing ilmenite, in the paramagnetic state above 49 K and magnetically ordered at 6 K, are observed. The average degree of oxidation of the ilmenites, estimated from the chemical analysis assuming ideally stoichiometric full cation site occupancies, is also confirmed by ⁵⁷Fe Mössbauer data. Since our crystal chemistry study gave no evidence of crypto-exsolution textures within the ilmenite with the observed compositions, fast cooling from magmatic temperatures and decomposition of ilmenite in supergene conditions is suggested.