Graft copolymers of rodlike cellulose nanocrystals (CNC) with poly(styrene) (PSt) were synthesized through atom transfer radical polymerization (ATRP). The hydroxyl groups on CNC were esterified with 2-bromoisobutyrylbromide to yield 2-bromoisobutyryloxy groups, which were used to initiate the polymerization of poly(styrene). The graft copolymers were characterized by thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The size of the original CNC is 10-40 nm in width and 100-400 nm in length. which was characterized by atomic force microscopy (AFM). The thermal and liquid crystalline properties of the graft copolymers were investigated by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). The graft copolymers exhibit fingerprint texture in both thermotropic and lyotropic states. In thermotropic state, the PSt-grafted CNC orient spontaneously in isotropic melt (PSt side chains acting as a solvent). The thermotropic liquid crystal phase behavior is similar to the lyotropic phase behavior. (c) 2008 Elsevier Ltd. All rights reserved.