The adhesion of electrodeposited metal film to polymeric circuit board substrate is one of the key elements to successful miniaturization of electronic devices. However, as the size of the circuit pattern continuously decreases, a novel method is urgently required to increase the adhesion of the metal film on the substrate, especially on the smooth surface, which is critical to decrease the minimum feature size of the metal pattern. In this research, we developed an adhesion promoter layer by depositing metal chelating poly(4-vinylpyridine) (P4VP) film onto various organic and inorganic substrates via initiated chemical vapor deposition process (iCVD) to enhance the adhesion between the electroless deposited copper (Cu) layer and the substrate. The highest peel strength obtained between the electroless deposited Cu layer and P4VP coated substrate was 1.22 kgf/cm. Many advantageous characteristics of the adhesion promoter layer, including extreme thinness, the improved adhesion strength, conformal coverage, scalability of the deposition process, and short process time, will prompt the applicability of this adhesion promoter layer to industrial scale production.