Calcium titanofluoride CaTiF5(s) was prepared by solid-state reaction of CaF2(s) with TiF3(s) and characterized by X-ray diffraction method. The standard molar isobaric heat capacity (C degrees(p,m)) of CaTiF5(s) was determined by a power compensated differential scanning calorimeter in the temperature from 230 K to 7 10 K. A solid-state galvanic cell with CaF2 as electrolyte was used to determine the standard molar Gibbs energy of formation (Delta(f) G degrees(m)) of CaTiF5 in the temperature range from 803 K to 1005 K. The galvanic cell can be depicted as: (-)Pt,O-2 (g, 101. 325 kPa) / {CaO(s) + CaF2 (s)} //CaF2 // {CaTiF5 (s) + CaTiO3 (s)}/O-2 (g, 101. 325 kPa), Pt(+) The second law analysis of present data were carried out to derive the standard entropy S degrees(m)(298.15 K) and the enthalpy of formation Delta H-f degrees(m)(298.15 K) and the values derived are 68.7 J . K-1 . mol(-1) and -2848.4 U . mol(-1), respectively. (c) 2006 Elsevier Ltd. All rights reserved.