Vanadium containing slurry is a by-product of vanadium pentoxide by hydrometallurgical methods from vanadium slag. It is promising technogenic raw material for vanadium production. The phase analysis of vanadium-containing slurry by X-ray diffraction method has shown that it contains vanadium in spinel form (FeO∙V2O3). The various oxidation roasting methods for slurry treatment have been studied for increasing vanadium extraction into the solution. It has shown that the most effective additive is 1% CaCO3 at a roasting temperature of 1000 °C. The oxidation roasting of vanadium-containing slurry with the additive led to increase acid-soluble form of V2O5 from 1.5 to 3.7% and decrease the content of FeO∙V2O3 from 3 to 0.4%. These results have confirmed the efficiency of the application of oxidation roasting to convert vanadium compounds into acid-soluble forms. The conversion mechanism of spinel to acid-soluble phases during oxidation roasting with additives was investigated by thermogravimetric analysis and thermodynamic simulation. It has shown that the formation of acid-soluble calcium vanadates during oxidation roasting without additives occurs at temperatures above 800 °C, but СаСО3 addition allows to reduce this temperature to 600 °C.