Based on the strong polymeric role of phosphate (PO3-4) on the PFS, PO3-4 was introduced in the ferric sulfate (PFS), and a new type of composite flocculant polymeric phosphate ferric sulfate (PPFS) was developed. The study includes the preparation of PPFS，and erric species distribution in PFSS was investigated by ultraviolet-visible spectrum method, infrared spectrum method and Fe-ferron complexation timed spectrophotometry method. The ultraviolet-visible spectrum showed that the change in the spectral curve of the different pH polymer ferric sulfate flocculants is corresponding to the flocculation morphology. Infrared spectra showed that the —P—O or PO vibration exists in the PPFS, certificated the ferric ion in PFS and phosphate caused the reaction, and produced the phosphate ferric polymer; and Fe-ferron complexation timed spectrophotometry showed that the amount of Fe(c) in polymeric phosphate ferric sulfate (PPFS) flocculants was the most in the three species, while the amount of Fe(a) and Fe(b) was small, that is PPFS mainly exists in the form of phosphate ferric polymer.