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An adherent polymer film based on a composite of polyacrylonitrile/multiwall carbon nanotubes (PAN/MWNTs) have been elaborated on a copper substrate. The first layer is an electrografted PAN brush on which of a subsequent layer of PAN/carbon nanotubes composite has been deposited by simple dipping from solution in dimethylformamide (DMF). MWNTs have been previously chemically functionalized with 3-cyanopropyltrichlorosilane to promote de-bundling and homogeneous dispersion of the carbon nanotubes in the composite.