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In this work, a series of amphiphilic hemicellulose-based grafting polymers are synthesized by homogeneous esterification with various hydrophobic chain fatty acids. With the flexible chain conformation of hemicelluloses, the hemicellulose-graft-fatty acid is self-assembled into hard sphere micelles in aqueous solution through hydrophobic interactions. The resultant micelles show apparent hydrodynamic radius (Rh) varying in the range of 34-57 nm and radius of gyration (Rg) varying from 30 to 44 nm. Moreover, the Rh, Rg, zeta potential a