Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and unfunctionalized. MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced the aromatic amine (COC6H4-NH2) groups on the side wall. The F-MWNTs were chemically bonded with the PCL chains in the F-MWNT/PCL, as indicated by the appearance of the amide 11 group in the FT-IR spectrum. The TGA thermograms showed that the F-MWNT/PCL had better thermal stability than PCL and P-MWNT/PCL. The PCL and the nanocomposite nanofibers were prepared by an electrospinning technique. The nanocomposites that contain more than 2 wt% of MWNTs were not able to be electrospun. The bead of the F-MWNT/PCL nanofiber was formed less than that of the P-MWNT/PCL. The nanocomposite nanofibers showed a relatively broader diameter than the pure PCL nanofibers. The MWNTs were embedded within the nanofibers and were well oriented along the axes of the electrospun nanofibers. as confirmed by transmission electron microscopy. (c) 2006 Elsevier Ltd. All rights reserved.