Direct covalent attachment of amorphous and semicrystalline polyetherketones onto the surface of either an as-received multi-walled carbon nanotube (MWNT) or a vapor-grown carbon nanofiber (VGCNF) in polyphosphoric acid (PPA) with optimized P2O5 content resulted in uniform grafting of polyetherketones to these carbon nanoscale materials. Soxhlet extraction experiment, the spectra from FT-IR spectroscopy and the clear images from high-resolution transmission electron microscopy showed that the covalent attachment is effective in uniformly coating the PEK grafts on the surfaces of both MWNT and VGCNF. Additionally, a drastic increase in solution viscosity due to the formation of giant molecules was monitored during polymerization. As such, the resulting nanocomposites were easily fabricated via a simple compression molding technique. The alignment possibility of MWNT and VGCNF grafted with semicrystalline PEK in these thermoplastic nanocomposites via solution fiber spinning was also demonstrated. (c) 2005 Elsevier Ltd. All rights reserved.