Ni-ferrite (NiFe 2O 4) has a lower reaction temperature for the O 2-releasing reaction when irradiation by a high-flux solar beam than that predicted by the estimation based on the thermodynamic data. The reaction mechanism of Ni-ferrite in the O 2-releasing reaction of a two-step water-splitting process at high temperatures (1,273–1,823 K) was clarified by means of X-ray diffractometry (XRD), extended X-ray absorption fine structure (EXAFS) analysis, Mössbauer spectroscopy and Magnetization measurement. The analysis of the EXAFS and Mössbauer spectra for Ni-ferrite before and after the O 2-releasing reaction shows that a lattice defect (Fe 3+ (B-site)⇒Fe 3+ (interstitial A-site)) intermediate with a spinel-type structure was formed in the early stage of the O 2-releasing reaction (up to 1,723 K). It is suggested that irradiation by a high-flux infrared beam resulted in the formation of the lattice defect intermediate with a Frenkel defect. The formation of the lattice defect intermediate with a Frenkel defect was due to the high reactivity of Ni-ferrite in the O 2-releasing reaction, as compared with other ferrites.