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To reduce the surface protein adsorption of polysulfone (PSf) film, we improved the hydrophilicity of this film by photochemical grafting of methoxypoly (ethylene glycol) (MPEG) derivatives on its surface. Grafting was achieved with both the simultaneous method and the sequential method. Surface analysis of the grafted film by X-ray photoelectron spectroscopy (XPS) revealed that the PEG chains had successfully grafted onto the surface of the film. The grafting efficiencies by simultaneous and sequential methods were 20.8% and 10.2%, respectively. With an atomic force microscope (AFM), the surface topography of PEG-grafted films by these two methods was compared. Static water contact angle measurement indicated that the surface hydrophilicity of the film had been improved. Protein adsorption measurement showed that the surface protein adsorption of the modified film was significantly reduced compared with that of the unmodified PSf film.