We introduce a novel method for producing polystyrene (PS)-grafted multiwalled carbon nanotubes (MWCNTs), which provides a direct route to composites where carbon nanotubes (CNTs) are the major component. Infrared and Raman spectroscopies confirmed that the MWCNTs were functionalized with PS. Thermogravimetric analysis showed that CNTs increase thermal stability of the composite up to a critical loading (∼40 wt%) beyond which high nanotube loadings decrease the polymer degradation temperature, as a consequence of the thermal properties of CNTs and the composite morphology. Even at loadings as high as 80 wt% MWCNTs, the composite is an effective masterbatch material for both solution- and melt-processing. These results show that in situ polymerizations can be flexible and robust techniques for nanocomposite processing, overcoming limitations of conventional processing techniques to produce nanocomposites with very high nanotube loadings, not achieved hitherto.