Abstract This research investigated water leaching of roasted vanadium slag and studied the effects of leaching parameters, such as agitation speed, temperature, liquid-to-solid ratio, and leaching time. Further, solution purification via desiliconization and precipitation of ammonium vanadate were studied using the vanadium solution obtained from the water leaching of roasted vanadium slag. Vanadium solution contains residual silicon (1.67 g/L), which should be removed before ammonium vanadate precipitation. Based on the results, vanadium can be effectively recovered from vanadium slag and a recovery efficiency of 96.9% was obtained under optimal water leaching conditions. During solution purification, silicon can be precipitated with Al2(SO4)3 to very low levels without any significant vanadium loss. The ammonium vanadate precipitation achieved a high precipitation efficiency of >99%.