The phase composition at the slag−iron interface and the distribution behavior of titanium, vanadium, chromium and silicon between hot metal and Ti-bearing electric furnace slag were thoroughly explored. The basicity range for the anosovite phase region was defined by using a phase diagram and a minimum smelting temperature was set at 1540 °C. Thermodynamic calculations demonstrate that the activities of TiO₂ and SiO₂ in the slag decrease with increasing basicity, while those of V₂O₃ and Cr₂O₃ increase. Similarly, the activities of [Ti] and [Si] in the molten metal decrease, while those of [V] and [Cr] rise with increasing basicity. As basicity increases, the distribution ratios, L_Ti and L_Si decrease, whereas L_V and L_Cr increase. Significantly, the recovery efficiencies of vanadium and titanium are improved with higher basicity. The primary phases identified in the slag include anosovite, diopside, and titanium spinel. However, when the basicity exceeds 0.8, the formation of the perovskite phase becomes less favorable, suggesting that basicity should be maintained at or below 0.8.