In this paper, we successfully combined three processes: selfassembled polyelectrolytes, catalyst ink-jet printing, and electroless metal plating technologies for the fabrication of electronic circuits. Poly (acrylic acid) (PAA) and poly (allylamine hydrochloride) (PAH) are primarily layer-bylayer adsorbed on the substrate. An inkjet-deposuted catalyst pattern binds by ion exchange to topped-surface PAH and forms metal nanoparticles. Finally, the electroless plating process form the electronic circuit on the pattern of catalyst. Besides, the process of immersing in acidic aqueous environments causes the microporous transformation. Therefore, due to the higher surface area and the microporous structure, these self-assembled polyelectrolyte layers are of great benefit to the absorption of the catalyst used for metal deposition. Hence, the above processes form excellent metal pattern for various substrate, like PET, Glass, PI, FR-4 etc.