A new kind of inorganic polymer flocculant, the solid composite polyferric sulfate (SPFS) was prepared using ferrous sulfate and Na-Bentonite. The obtained SPFS was characterized by FT-IR spectra, thermogravimetric analysis (TG), scanning electron microscope (SEM) and X-ray Diffraction (XRD). It showed that SPFS was a kind of composite inorganic polymer, which was the complex of PFS and Na-Bent, not only a simple mixture of raw materials. The synthetic mechanism and surface structure of SPFS were also discussed. Acting as a kind of environment-friendly flocculating agent, the solid composite polyferric sulfate (SPFS) was applied in pretreatment of potato starch industry wastewater, a typical wastewater containing high concentration organic compounds, which COD was above 6,000 mg/L. The results showed that the COD removal value reached 4,070 mg/L with COD removal rates being 46.6%. Based on these results, it is suggested that the SPFS can be attractive pretreatment agent for the starch industry wastewater.