Effective functionalization of multi-walled carbon nanotubes (MWCNTs) with styryl group was carried out via the esterification reaction of the carboxylate salt of carbon nanotubes and 4-vinylbenzyl chlorides in toluene. The functionalized MWCNTs were characterized through FTIR and Raman spectra to confirm the styryl groups covalently connected to the surface of MWCNTs. The weight loss of functionalized moieties determined by thermogravimetry-differential scanning calorimertry analysis is around 36%. Nanotube-reinforced polystyrene were fabricated by mixing functionalized MWCNTs and polystyrene. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the functionalized nanotubes had a better dispersion than the unfunctionalized MWCNTs in the matrix. Moreover, styryl-modified MWCNTs/PS nanocompsite presented obvious improvements in mechanical properties and thermal stability.