Enthalpy increment of CS80Bi20 liquid alloy in the temperature range of 857–1076 K was measured by mixing method on a massive calorimeter with an isothermal shell. The heat capacity of the melt was determined and it was found that for the studied temperature range it remains constant, and its absolute value exceeds significantly the calculation by the additivity rule. The estimated errors for enthalpy and heat capacity of the melt were 0.4 and 1%, respectively. An approximation equation was obtained for the dependence of the mass heat capacity of the solid alloys of the cesium-bismuth system at 298.15 K by the atomic concentration of bismuth.