The constant-volume energy of combustion of crystalline anhydrous caffeine (C8H10N4O2) in alpha (lower temperature steady) crystal form was measured by a bomb combustion calorimeter, the standard molar enthalpy of combustion of caffeine at T = 298.15 K was determined to be -(4255.08 +/- 4.30) kJ (.) mol(-1), and the standard molar enthalpy of formation was derived as -(322.15 +/- 4.80) kJ(.)mol(-1). The heat capacity of caffeine in the same crystal form was measured in the temperature range from (80 to 387) K by an adiabatic calorimeter. No phase transition or thermal anomaly was observed in the above temperature range. The thermal behavior of the compound was further examined by thermogravimetry (TG), differential thermal analysis (DTA) over the range from (300 to 700) K and by differential scanning calorimetry (DSC) over the range from (300 to 540) K, respectively. From the above thermal analysis a (solid-solid) and a (solid-liquid) phase transition of the compound were found at T = (413.39 and 509.00) K, respectively; and the corresponding molar enthalpies of these transitions were determined to be (3.43 +/- 0.02) kJ(.)mol(-1) for the (solid-solid) transition, and (19.86 +/- 0.03) kJ(.)mol(-1) for the (solid-liquid) transition, respectively. (c) 2006 Elsevier Ltd. All rights reserved.