The detailed crystal chemistry of ilmenite from the Hadong massif was studied by the EPMA, M ssbauer spectroscopy, and Rietveld structural refinement using X-ray powder diffraction data. The ilmenite-bearing anorthosite shows complicated mineral assemblage which consists of plagioclase, clinopyroxene, hornblende, biotite, chlorite, apatite, allanite, and zircon. Anorthite is andesine in composition (Ab 28-57), and clinopyroxene drops in ferro-hypersthene (Fs 62-70). Ilmenite is trigonal symmetry with R space group, whose structure shows the alternation of Fe2+ (M1 site) octahedral layer and Ti (M2 site) layer along c axis. M ssbauer spectroscopy indicates that there are three doubles which assigned to couple of Fe2+(δ=0.812, 0.890mm/sec) and one Fe3+(δ=0.303mm/sec) in octahedral sites. Their Fe3+/ΣFe is 0.065 and chemical formula is established as Fe2+0.94Fe3+0.07Ti0.97O3 using both EPMA and M ssbauer analysis. Rietveld structural refinement reveals that site occupancies of Fe in M1 and Ti in M2 are 91.2% and 89.4%, respectively. This implies that Ti and Fe2+ are alternatively occupy M1 and M2 sites. In addition, smaller M2 site is more preferable to Fe3+ occupancy over M1.