Vanadium–titanium-bearing direct reduced iron (V-Ti DRI) is a promising feedstock for the full-value utilization of V-Ti magnetite. Selective partition of V and Cr into the metal phase, with Ti retained in the slag, requires quantitative thermodynamic guidance. We investigate this slag–metal distribution using the ion and molecule coexistence theory (IMCT). An eight-component slag model with 33 complex-molecule equilibria is coupled to reduction thermodynamics through an iterative mass-balance procedure; the metal-phaseWagner activity is temperature-scaled by Chipman’s rule, and the dissolved oxygen concentration is closed through the C-CO-O equilibrium. The equilibrium V and Cr recovery ceilings (metal side) rise from 89%/96% at 1400 °C to approximately 99.4% at 1500 °C and exceed 99.8% at 1550 °C. Ti-in-slag retention (slag side) drops steadily from 99.998% at 1400 °C to 99.4% at 1700 °C, giving a V/Ti separation factor above 104. Fe recovery to the metal phase exceeds 97% at 1600 °C and above, driven by the strong reduction of FeO, which constitutes approximately 32 wt.% of the initial slag. Carbon activity exerts a cubic power-law effect: at 1450 °C, the V recovery ceiling collapses from 97.4% at a_C = 1 to 6.5% at a_C = 0.05, identifying imperfect carbon saturation as a primary thermodynamic mechanism behind the ceiling-to-pilot gap. Once temperature and oxygen closure are enforced, the ceilings are only weakly sensitive to metallization, basicity, coke ratio, and TiO₂ content. Comparison with pilot data shows the ceilings exceed reported yields by 16–29 percentage points (pp), quantifying the kinetic/mass-transfer deficit and providing a benchmark for scale-up.