Methods of isolating tungsten and, in particular, methods of separating tungsten and vanadium are described herein. The methods can generally comprise treating a tungsten-containing material in aqueous solution with a reducing agent suitable for the reduction of pentavalent vanadium to one or more lower oxidation states of vanadium, such that the tungsten can be more readily separated from the vanadium, e.g., via solvent extraction. In certain embodiments, the methods disclosed herein can provide tungsten, vanadium, or both tungsten and vanadium in sufficient purities for commercial use.