The surface hydrophobicity/hydrophilicity of ramie fiber was regulated through the atom transfer radical polymerization of methyl methacrylate from initiators immobilized on the fiber. The optimal reaction conditions for preparing the macroinitiated ramie fiber were determined to be a temperature of 60 degrees C and a reaction time of 24 h. The grafted copolymers were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy-dispersive analysis of X-rays, gel permeation chromatography, and thermogravimetric analysis. The results indicate that poly (methyl methacrylate) was covalently bonded onto the surface of the ramie fiber, and the polymerization of methyl methacrylate was a living/controlled process under the investigated conditions. The results of the contact angle measurements indicate that the wettability of the ramie fiber could be widely regulated by control of the grafted ratios of poly(methyl methacrylate) from 26 to 33 wt %. (C) 2008 Wiley Periodicals, Inc.