The heat capacity of ilvaite from Seriphos, Greece was measured by adiabatic shield calorimetry (6.4 to 380.7 K) and by differential scanning calorimetry (340 to 950 K). The thermal expansion of ilvaite was also investigated, by X-ray methods, between 308 and 853 K. At 298.15 K the standard molar heat capacity and entropy for ilvaite are 298.9??0.6 and 292.3??0.6 J/(mol. K) respectively. Between 333 and 343 K ilvaite changes from monoclinic to orthorhombic. The antiferromagnetic transition is shown by a hump in Cp0with a Ne??el temperature of 121.9??0.5 K. A rounded hump in Cp0between 330 and 400 K may possibily arise from the thermally activated electron delocalization (hopping) known to take place in this temperature region. ?? 1988 Springer-Verlag.