The structural change of Fe2C by mechanical alloying of elemental powders was studied with X-ray diffraction and Fe-57 Mossbauer spectroscopy. X-ray diffraction pattern changed from bcc alpha-Fe to the orthorhombic Fe3C in the first stage of milling and to the hexagonal phase in the second stage. Amorphous phase was not obtained. Fe-57 Mossbauer spectra changed from alpha-Fe, H-int.=330 kG, to a ferromagnetic sextet, H-int.=205kG, in the first stage and split into two ferromagnetic ones, H-int.=165 and 210kG in the second stage. The atomic distance between Fe atoms for the hcp phase prepared by mechanical alloying was 2.57Angstrom, which was larger than that of the high pressure hcp epsilon-Fe.