Polyacrylonitrile (PAN) fiber was grafted with casein after alkaline hydrolysis and chlorination reactions of the original fiber. The structures and morphologies of the casein grafted fiber were characterized by Fourier transform infrared spectroscopy (FTIR), X-Ray diffraction (XRD), and scanning electron microscope (SEM). Moisture absorption, specific electric resistance, water retention value, and mechanical properties were also investigated. The results showed that casein was grafted onto the surface of the PAN fiber and the grafted PAN fiber presented better hygroscopicity compared with the untreated fiber. With proper tensile strength, the modified fiber could still meet the requirement for wearing. A mechanism was proposed to explain the deposit of casein on the synthetic acrylic fiber.