Two different crystals of 1’,1 triple prime-dihexylbiferrocenium triiodide were obtained from the different solution (hexane or dichloromethane). The salt prepared from hexane has a longer interlayer distance and gives frapped-valence state of Fe atoms, while the salt recrystallized from dichloromethane has a shorter interlayer distance and gives typical fusion-type valence detrapping of the mixed-valence state on the Fe-57 Mossbauer spectroscopy. By annealed at 323 K the latter changes into the former salt. The X-ray diffraction study of the latter supports the results of the Fe-57 Mossbauer spectroscopy.