A mild and facile way was used to prepare poly(nitriloethylenenitrilovinylene)-grafted multi-walled carbon nanotubes (MWCNTs-g-PNENV) nanocomposites via the “grafting to” method. The MWCNTs-g-PNENV nanocomposites are well dispersible in polar solvents such as water, tetrahydrofuran and ethanol. Chemical structure of the resulting product was characterized by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA). FTIR showed that the “grafting to” process belonged to covalent attachment mechanisms. TEM observations indicated that the MWCNTs were coated with a uniform PNENV layer, and the MWCNTs existed as a hard backbone. TGA data also showed that the PNENV shell was successfully grafted to the side wall of MWCNTs.