The solubility of vanadium oxide in the SiO2–CaO–VOX system was investigated as a function of basicity (CaO/SiO2) at a fixed temperature of 1600°C and oxygen partial pressure of 10−10 atm. Formed phases and microstructures of saturated samples were identified with SEM–EDS analysis and XRD. Maximum solubility of vanadium oxide was between 15 and 20% independent of basicity. Pure karelianite (V2O3) was formed in all samples at saturation of vanadium oxide. The morphology of karelianite changed with the change in basicity in the slag, where needles or threads were formed for slags with basicity B2 = 0.54 and B2 = 0.67 and stars or dendritic patterns were formed with basicity B2 = 1.0 and B2 = 1.22. Wollastonite (CaSiO3) was also formed in the slags with star or dendritic patterns.