A comprehensive analysis of the thermochemical properties of levoglucosan, using static bomb combustion calorimetry, Knudsen effusion technique, and differential scanning calorimetry, is presented. The experimental results allow us to derive the enthalpy of formation, in the gaseous phase, and thereafter to do a comparison with the same parameter obtained computationally. The good agreement between the experimental,, and computational results gives confidence to our determinations, particularly when they are compared with others already reported in literature. After testing the computational methodology, the ionization energy, electron affinity, proton affinity, gas-phase basicity, gas-phase acidity, and bond dissociation enthalpies of levoglucosan were also obtained. The presence of intramolecular hydrogen bonds in the most stable conformation of levoglucosan was verified by applying Quantum Theory of Atoms in Molecules calculations. Furthermore, a joint differential scanning calorimetry and temperature dynamic Fourier transform infrared (FT-IR) spectroscopic study was used to study the crystalline phase of levoglucosan between 298.15 K and the melting