Phase transformation from orthorhombic HfV 2 structure to cubic C15 Laves phase structure, which occurs during heating at about 114 K, is well known. In this contribution, a thermodynamic description of this phenomenon is provided supported by ab initio calculations. We utilize the third generation of thermodynamic database extending the Scientific Group Thermodata Europe (SGTE) unary data to zero Kelvin and demonstrate that it may be also applied to intermetallic phases. The data from a recent thermodynamic assessment of the Hf-V system (valid for temperatures above 298.15 K) were used and extended to zero Kelvin by the same method as it was used for unary data. Under the assumption of validity of harmonic approximation and electronic contribution to the heat capacity, the thermodynamics of C15 and orthorhombic phase were described. With the help of ab initio approach, we demonstrate that the HfV 2 orthorhombic phase and C15 Laves phase are mechanically stable at 0 K and thanks to entropy stabilization they are in equilibrium with pure element phases in the temperature region of structural change.