The multivalence of vanadium in oxide melts is considered. It is shown that the vanadium oxidation state in the slags is determined by the slag and metal compositions as well as the oxidation potential of the gas phase. Using a polymer model, vanadium valence form fractions were calculated depending on technological parameters. Calculations show that in an air atmosphere, vanadium in the slag should be predominantly in the tetravalent and trivalent state, and in contact with the molten iron, mainly in the trivalent and partly divalent state. Upon contact with pig iron, VO oxide becomes the main form of vanadium in the slag. Slag basicity and temperature have a significant effect on the relationship of vanadium forms. The suggested design-basis using the polymer model can be useful in accomplishment of the thermodynamic calculations for the vanadium equilibrium distribution between metal and slag in the iron and steel production. It allows us to describe the dependence of the vanadium oxidation state on the free oxygen activity in the slag and the gas phase oxidation potential.