AbstractCellulose-graft-poly(methylmethacrylate) (cellulose-g-PMMA) copolymers were prepared by homogeneous atom transfer radical polymerization (ATRP) under mild conditions, in an attempt to develop an efficient way to modify the surface of cellulose. A cellulose macro-initiator was successfully synthesized by direct homogeneous acylation of cellulose with 2-bromopropionyl bromide in a room temperature ionic liquid (RTIL), 1-allyl-3-methylimidazolium chloride ([AMIM]Cl). Copolymers were obtained via ATRP of methyl methacrylate (MMA) with CuBr/penta-methyldiethylenetriamine (PMDETA) as catalyst and N,N-dimethyl-formamide (DMF) as solvent without homopolymer byproduct. The grafting copolymers were characterized by 1H-NMR, 13C-NMR, and FTIR. The grafted PMMA chain was obtained by the hydrolysis of the cellulose backbone and analyzed by GPC and TGA measurements. In addition, the assemblies or aggregates formed by cellulose-g-PMMA copolymers were studied by means of TEM and AFM. The results indicated that the graft polymerization occurred from the cellulose backbone and the obtained copolymers had grafted polymer chains with well-controlled molecular weight and polydispersity; the cellulose graft copolymer in solution could aggregate and self-assemble into sphere-like structures.