Abstract <p>The experimental literature data on the thermal stability and fluorinating ability of cerium(IV) fluoride have been critically reviewed. Based on experiments involving the co-fluorination of CeF₃(cr) and platinum, the value of Δ_<i>f</i><i>H</i>^o(CeF₄, c, 298 K) = –1939.9 ± 7.6 kJ/mol was determined. The most reliable value for the sublimation enthalpy of cerium tetrafluoride was selected as Δ_s<i>H</i>^o(CeF₄, 298 K) = 270.2 ± 1.7 kJ/mol, and the formation enthalpy was calculated as Δ_<i>f</i><i>H</i>^o(CeF₄, g, 298 K) = –1669.6 ± 7.8 kJ/mol. A comparison of CeF₄(cr) with other solid-phase fluorinating agents was carried out.</p>