We investigated the thermal reduction (T-R) of NiFe2O4, either supported by m-ZrO2 or unsupported, as the oxygen-releasing step of a solar thermochemical water splitting cycle based on a ferrite/wustite redox system, by performing the Rietveld analysis using powder X-ray diffraction. The solid materials obtained after the T-R step at 1300-1400 degrees C were subjected to Rietveld analysis. The amounts and chemical compositions of the wustite phase produced by the T-R step and the remaining ferrite phase were identified quantitatively. Chemical reaction formulas for the different T-R temperatures were determined from the results. Consistency for the chemical reactions of the thermal reduction was discussed and evaluated comparing the O2 amounts predicted by the chemical reaction formulas and measured experimentally by mass spectrometry. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.