In this paper polyamidoamino (PAMAM) dendrimer synthesized on the solid surface of poly ethylene terephthalate (PET) film through repetitive Michael addition and amidation reactions is reported. Before the synthesis, the amino groups were grafted on the PET surfaces using a dielectric barrier discharges (DBD) at atmospheric pressure with ammonia as a monomer. Then with the grafted amine as core the polyamido amino was synthesized on organic PET solid film surface. The dendrimer structures were then characterized by Fourier transform spectroscopy (FTIR) and ¹H nuclear magnetic resonance (NMR), and the surface morphology was scanned by atomic force microscopy (AFM). This strategy provides a novel way to modify the film surface by combining plasma technology and chemical reaction. It shall be benefit for biosensor, biomedical, catalyst, photonic crystal, plasmonic crystal, and magnetic domain applications and so on.