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The heat capacities of (NH4)3[FeF6] crystal have been measured from 15 to 350 K with an adiabatic calorimeter. A heat capacity anomaly was observed at 267.02±0.05 K. The enthalpy and entropy changes of the transition are 6490±500 J mol−1 and 24.8±1.9 J K−1 mol−1, respectively. This value of entropy was discussed in terms of a model involving orientational disorder of the ammonium as well as hexafluoroferrate(III) ions. Based on the assumption of the average fcc symmetry of the crystal and internal rigidity of the ions, the proposed model predicts the transition entropy equal to R In 16=23.05 J K−1 mol−1 which is in close agreement with the experimental value. Temperature dependent splitting of the Raman band due to the internal vibration of the anion was found to be consistent with the model. The excess heat capacity follows the prediction of the Landau theory of phase transitions of the second kind. Properties of the present and the similar crystals including ammonium and alkali salts of hexafluoro-complex ions were discussed in terms of the ionic orientational disorder.