The heat capacity of the solid solution of trimethylolpropane and pentaerythritol(60:40 mol%)was measured by means of an automated adiabatic calorimeter. A solid-solidtransition and a melting transition of the solid solution were found at 330.51 K and433.0 K with the transition enthalpies of 9.72 and 5.76 kJmol-1, respectively.