Surface modification of carbon fibre (CF) by well-defined polymer brushes was carried out using the 'grafting from' method. Poly(methyl methacrylate)-grafted carbon fibre (CF-PMMA) was successfully prepared by surface-initiated atom-transfer radical polymerization (SI-ATRP) of methyl methacrylate (MMA) from the macro-initiator, bromo-acetic ester-modified carbon fibre (CF-BrA), with the complex of 1,10-phenanthroline and Cu(I)Br as catalyst. The percentage of grafting (PG%) and the conversion of monomer (C%) increased linearly with increasing of polymerization time, and reached 24.0% and 6.7%, respectively, after a polymerization time of 6 h, calculated from the elemental analyses (EA). The structural and surface morphological analyses were conducted with Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). (c) 2005 Society of Chemical Industry.