The possibility of applying a hyperbolic model for calculating thermodynamic characteristics (the standard molar heat capacity, standard molar entropy) to the V–O system is shown. For calculation of the molar specific heat and entropy within the bounds of the model the general concept has been used: a thermodynamic parameter is divided into two components. The first component depends on the molar mass of a compound, the second one is determined by inter particle interaction. The dependence of the inverse value for the interaction heat capacity (entropy) on composition is of linear character within one region of quasi-equilibrium solid solutions (one region combines compounds with the same or similar structure type).The use of the model allowed refining the available experimental data on vanadium oxides and predicting the values of thermodynamic characteristics for compounds poorly studied in experiment.