A well-dispersed multiwall carbon nanotube (MWCNT)/syndiotactic polystyrene (sPS) composite was prepared by simple in-situ polymerization of styrene using pentamethylcyclopentadienyltitanium(IV) trimethoxide (Cp*Ti(OMe)(3)) attached to the shortened and functionalized MWCNT (f-MWCNT). The attachment of Cp*Ti(OMe)(3) to the f-MWCNT was confirmed by thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy, and energy dispersive X-ray spectroscopy. Cp*Ti(OMe)(3) attached to pristine MWCNT in the presence of methylaluminoxane (MAO) did not produce PS, whereas Cp*Ti(OMe)(3) attached to f-MWCNT showed a high catalytic activity for the syndiospecific polymerization of styrene under the same polymerization conditions. Obtained sPS showed a narrow molecular weight distribution (PDI approximate to 2), a high SI value (>= 90%), and a high melting point (approximate to 272 degrees C). Scanning electron microscopy and transmission electron microscopy images showed that MWCNT strands were well dispersed in the MWCNT/sPS composite. Such composites had greatly improved thermal stability compared to normal sPS polymers. (C) 2012 Elsevier Ltd. All rights reserved.