The synthesis and characterization of a novel natural-synthetic hybrid material based on cellulose is reported. The reversible addition-fragmentation chain-transfer (RAFT) process was used to graft poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) onto a cellulosic substrate. The weight ratio was increased with an increase in monomer concentration, polymerization time and degree of polymerization (DP). We found that the addition of free chain-transfer agent has a pronounced effect on the weight ratio, chain length of grafted polymer, monomer conversion and homopolymer formation in solution. The cellulose-graft-poly(2-(dimethylamino)ethyl methacrylate) copolymers were characterized by gravimetry, elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, thermal analysis and atomic force microscopy. The dithioester end-group present at the chain end of PDMAEMA was removed via aminolysis. The livingness of the process was utilized to block-copolymerize styrene from the grafted PDMAEMA chains. The hydrophilic/hydrophobic properties of the novel cellulose-g-(PDMAEMA-b-polystyrene) material were illustrated by contact-angle measurements.