This Article describes for the first time the formation of a supramolecular self-assembled monolayer of polymeric phthalocyanine (poly(CuPc)) onto a gold substrate. The latter is established through the interaction of the cyano group, belonging to the poly(CuPc), with the metal substrate. The functionalized gold substrate was characterized using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical methods. Results clearly demonstrated the interaction between gold and the nitrogen atom of cyano group and showed tit the so ire time the formation of a completely covered polymeric monolayer on the gold surface. In addition. the modified gold surface seems to exhibit a reversible redox behavior and is found to act as an electronic conductor. which allows rapid electron transfer. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN6)(3-) (4-) as redo couple revealed that the modified electrode showed a much lower electron transfer resistance compared with hare gold. In addition, the modified electrode is found to catalyze the H2O2 reduction very effectively, showing a catalytic current that varies linearly with the peroxide concentration in the range of 0.35 to 70 mu M with a detection limit of 0.25 mu M.