The vaporization of vanadium pentoxide from CaO-SiO2-VOx ternary slags using different gas treatment regimens and parallel vacuum gas extirpation to treat V-bearing slags at 1873 K has been developed in the present study. The novelty of the present study is to monitor the effect of parallel alumina dissolution on the vaporization phenomenon. Vanadium pentoxide has high vapor pressure at the temperatures over 1500 K. When CaO-SiO2-VOx ternary slags, kept in dense alumina crucibles, are injected with oxygen, V2O5 gas bubbles are formed which are forced out by using vacuum extirpation. The vanadium pentoxide could be then collected in the exhaust gases. The mechanism of the process phenomenon is described as the formation of V2O5 gas phase resulting from the oxidation of the lower-valent oxides present in the slag. This gas phase would form microbubbles in the molten slag bulk phase due to low surface tension between the gas phase and the slag, thereby increasing the contact surface. At the same time, the crucible material would dissolve in the slag causing an increase in the slag viscosity. Due to the high slag viscosity of the bulk slag, these microbubbles formed would have difficulty in coalescing and reaching the slag surface. The escaping of the bubbles into the gas phase is enabled by the vacuum extirpation.