Surface thermal graft copolymerization with concurrent lamination was carried out between an Ar plasma pretreated poly(vinylidene fluoride) (PVDF) him and a copper foil in the presence of a small quantity of a N-containing monomer, such as 4-vinyl pyridine (4-VPN) and acryloyl morpholine (ACMO), under atmospheric conditions and in the complete absence of an added polymerization initiator and system degassing. The adhesion strength, as reported by T-peel strength, was dependent on the argon plasma pretreatment time of the PVDF film, the thermal lamination temperature and the type of monomer. An optimum T-peel adhesion of about 10 N/cm was readily achieved in the Cu/PVDF laminate for grafting and lamination carried out in the presence of 4-VPN. A lower adhesion strength was obtained using ACMO and other N-containing monomers. The chemical compositions of the graft copolymerized and delaminated sample surfaces were studied by X-ray photoelectron spectroscopy (XPS). The failure mode of the Cu/4-VPN/PVDF assembly was a combined adhesional and cohesive failure. The strong adhesion between the Cu foil and the PVDF film arises from the strong charge transfer interaction between Cu and the pyridine ring, as well as the fact that the graft chains are covalently tethered on the PVDF films surfaces as a result of surface graft copolymerization.