A novel process for treating pickling acid residue and recovering sulfates and nickel therefrom has been developed. By lowering the pH of a magnesium compound slurry to 4-5.5 with sulfuric acid containing pickling acid residue in the presence of ammonium sulfate, both magnesium sulfate and nickel sulfate are solubilized. Magnesium sulfate and nickel sulfate solution is separated from the solids by filtration and an iron hydroxide and chromium hydroxide residue is obtained as a precipitate. Magnesium sulfate and nickel sulfate are then separated from the solution.