In addition to properties such as biocompatibility and biodegradability, cellulosic natural fibers have a higher strength property than the synthetic polymers and glass fibers. So they are suitable alternatives to synthetic and glass fibers. However, cellulose is highly hydrophilic and has low reactivity. Therefore, its industrial applications are limited. To overcome such drawbacks, the chemical modification of the cellulose structure is necessary. Graft copolymerization, a commonly used method for the modification of polymer surfaces, can be applied as an important tool for modifying the physical or chemical properties of polymers. By grafting hydrophobic polymer chains onto the cellulose fiber surface, the hydrophilicity of the cellulose can be altered. In this project, polyacrylonitrile was grafted onto cellulose surface by atom transfer radical polymerization (ATRP) technique. In the first step, the reaction of OH cellulosic groups with acryloyl chloride in the LiBr/N,N-dimethyl acetamide mixture was carried out to form pendant double bonds and yield water soluble cellulose acrylate. Then, 4-chloromethyl styrene in the presence of toluene was grafted onto the unsaturated group via free radical polymerization and using azobisisobutyronitrile as the initiator. Finally, the synthesized cellulose-graft-polychloromethyl styrene having a transferable atom (Cl) for the polymerization of acrylonitrile in THF and in the presence of copper (I) chloride /2,2’-bipyridine as a catalyst system was used as an ATRP macroinitiator to prepare the cellulose-graft-polychloromethylstyrene-graftpolyacrylonitrile terpolymer. The products were characterized by scanning electron microscopy, X-ray diffraction and FTIR spectroscopy and their thermal stability was investigated by the thermogravimetric analysis and differential scanning calorimetry.