Multi-walled carbon nanotubes (MWNTs) ha been successfully modified with polyacrylonitrile (PAN) a cathodic electrochemical process. The surface-modified MWNTs afforded are then dispersible in good solvents PAN, such as N,N-dimethylformamide (DMF). Collect from a dilute dispersion, these MWNTs are essentially disentangled, as confirmed by transmission electron microscopy (TEM) analysis. From the differential scanning calorimetry (DSC) traces for polyacrylonitrile and polyacrylonitrile-grafted MWNTs, the maximum grafting ratio is estimated at 0.28.