Selenium (Se) is an elementary trace nutrient element for human but there is a very narrow range between deficit and toxic levels. Furthermore, excessive intake of Selenium is harmful for human. The product species of selenite which was removal by pyrite particles was studied in the present research. In the experiments, the pyrite particles were prepared by the wet ball mill method, and surface analyses of pyrite before and after contact with Se(IV) were conducted using X-ray photoelectron spectroscopy (XPS). Besides, the prepared pyrite samples were also characterized using both X-ray diffraction (XRD) and scanning electron microscope (SEM). X-ray diffraction analysis indicated that the purity of the prepared pyrite particles was above 97%, and the characteristic diffraction peaks of the particles well matched with that of FeS2 crystalline. Scanning electron microscope determination showed the shape of the particles was approximate ball and the size was range from 80 to 180 nm. And thus the pyrite particles prepared by the wet ball mill method had less particle size, larger specific surface area and higher reactive ability. The batch experiments exhibited the pyrite particles were able to remove 95% of Se(Ⅳ) (20 mg·L-1) from water within 12 hours. And the kinetic tests indicated reaction process between pyrite and Se(Ⅳ)fits a pseudo-first order kinetic model, which gives a pseudo-first order rate constant(kobs) of 0.26 h-1. XPS analyses were using the XPSPEAK program which has a Gaussian Lorentzian function. The results clearly displays that Se(Ⅳ) prefer to react with the surface-bound S2-2 rather than reacted with the surface-bound Fe2+ of pyrite particles. From XPS graph, it can be seen that the binding energy of sulfur element and iron element composed of pyrite shifted to the left a little, which means expensive state of sulfur element and iron element appeared on the pyrite surface. Analysis of the oxidation state of Se on the surface of pyrite particles by X-ray photoelectron spectra showed evidence for the reduction of Se(Ⅵ) to insoluble element Se(0) species. Besides, a spot of Se(Ⅳ)was existence on the surface of pyrite particles. The calculation results displayed that zero-valent selenium was dominant. At that, redox reaction was the main process when removal of Se(Ⅳ)in aqueous environment with pyrite, along with sorption reaction at the same time. The results of removal of Se (Ⅳ) in groundwater using pyrite offer important theoretical value and practical significance.