Multi-walled carbon nanotubes (MWNTs) were modified with poly(hexamethylene adipamide) (also known as Nylon 66) via a controlled polymer solution crystallization method. A "nanohybrid shish kebab" (NHSK) structure was found wherein the MWNT resembled the shish while Nylon 66 lamellar crystals formed the kebabs. These Nylon 66-functionalized MWNTs were used as precursors to prepare polymer/MWNT nanocomposites. Excellent dispersion was revealed by optical and electron microscopies. Nitric acid etching of the nanocomposites showed that MWNT formed a robust network in Nylon 66. Non-isothermal DSC results showed multiple melting peaks, which can be attributed to lamellar thickness changes upon heating. The crystallite sizes L-100 and L-010 of Nylon 66, determined by WARD, decreased with increasing MWNT contents. Isothermal DSC results showed that crystallization kinetics increased first and then decreased with increasing MWNT contents in Nylon 66. This study showed that the effect of MWNTs on Nylon 66 crystallization is twofold: MWNTs provide heterogeneous nucleation sites for Nylon 66 crystallization while the tube network structure hinders large crystal growth. (C) 2007 Elsevier Ltd. All rights reserved.