The standard molar enthalpy of formation of the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide has been determined at 298 K by means of combustion calorimetry, while the enthalpy of vaporization and the mass spectrum of the vapor (ion pairs) have been determined by temperature-programmed desorption and line of sight mass spectrometry. Ab initio calculations for 1-butyl-1-methylpyrrolidinium dicyanamide have been performed using the G3MP2 and CBS-QB3 theory, and the results from homodesmic reactions are in excellent agreement with the experiments.