For the metallurgical industries, the safe disposal of arsenic-bearing waste is animportant issue. In this study, a two-stage arsenic precipitation process was proposed, which consists of formation of scorodite at lower pH followed by precipitation of arsenical ferrihydrite at higher pH. The experimental results show that arsenic can be removed effectively from a solution with arsenic concentration of 5 g/L as precipitate of crystalline scorodite through oxidizing ferrous ions with air stream at pH of 2at first. Then, the pH value was raised to 3 and 4, and almost all the residual arsenic was removed from the solution due to adsorption onto amorphous ferrihydrite at the molar ratio of Fe/As between 2 and 4. The United States Environmental Protection Agency's Toxicity Characteristic Leaching Procedure tests demonstrate that the complex precipitates generated under these conditions (Fe/As ratio of 4, final pH between 3 and 4) were very stable and no leached arsenic can be detected using acetic acid buffer solution (pH 4.93 +/- 0.05) in tests of 72 h. Experimental results suggest that a high Fe/As ratio was necessary, so that the excess iron promotes the formation a product of good stability, arsenical ferrihydrite (AsFH: AsO43-center dot Fe(OH)(H2O)(1+x)) under a relatively high pH in acidic solution.