Sodium-jarosite is a type of industrial waste that results from hydrometallurgy and inorganic chemical production. The iron content of jarosite residue may be utilized to produce theoretically the ferrous materials. The difficulty in production of high quality poly-ferric sulfate (PFS) is how to remove impurities contained in jarosite residue. This paper proposes a novel method for disposing sodium-jarosite which can be used to synthesize PFS, a very important reagent for treating waste water. The method consists of a two-step leaching experimental procedures. The first step, pre-leaching process, is to remove impurity metals by strictly controlling the leaching conditions. The acid concentration of acidic water was adjusted according to the content of impurity metals in sodium-jarosite and the leaching temperature was controlled at 25°C. The second step is to decompose sodium-jarosite to provide enough ferric ions for synthesizing PFS, the concentrated sulfuric acid consumption was 0.8 mL·g sodium-jarosite and the leaching temperature was above 60°C. In the experiment, decomposing iron from sulfate sodium-jarosite can take the place of ferric martials for synthesizing PFS. Results show that the PFS synthesized from sodium-jarosite had a high poly-iron complex Fe (SO ) (OH) ·20H O. Further, the PFS product’s specifications satisfied the national standard of China.