The possibility of using an acidic autogenous hydrogen direct reduced iron (H-DRI) slag as a basis for vanadium extraction is investigated. For a raw material to be suitable for producing high-quality FeV, the vanadium oxide content should be sufficiently high and the phosphorus oxide content in a tolerable range. Therefore, the feasibility for vanadium extraction relies on fulfilling two demands: the predominate partitioning of phosphorus to the metal and vanadium to the slag. Correspondingly, the behaviours of phosphorus and vanadium in the Al2O3-SiO2-FeOx-VyOz-P2O5-Fe system were studied experimentally. Slag, 10 g, was put in contact with liquid iron, 30 g, for different durations (2–24 hrs) in closed alumina crucibles at 1873 K. The slag composition was varied between 33.1– 49.3 wt per cent Al2O3, 27.1–46.7 wt per cent SiO2, 16.6–30.1 wt per cent FeOx, and 2.5– 8.8 wt per cent V2O3. The equilibrium phosphorus distribution was 0.42, while the vanadium distribution ranged from 7.6 to 43.4, increasing with the Al2O3- and the FeOx-content.