The invention disclosed provides a process for recovering niobium values from aqueous hydrofluoric acid solutions by evaporating said solution to dryness and baking the residue at temperatures of 150.degree. to 250.degree. C. The solid residue is niobium oxyfluroide (NbO.sub.2 F) which may then be exothermically reduced with aluminum in the presence of an alloying element such as iron, nickel, or chromium to produce a niobium alloy. The evaporated hydrofluoric acid may be recovered by condensing or absorbing the evolved vapors.