The formation of a binary porphyrinic self-assembled system between meso-tetrakis(4-carboxyphenyl) porphyrin (TCPP) and meso-tetrakis(4-dimethyl amino) porphyrin (TDAP) was easily designed through non-covalent interactions in solution and adsorbed on a gold substrate. It was found that non-covalent interactions and geometrical conformations between porphyrins allow their self-assembly into a well-defined arrangement, which was confirmed by UV-Vis spectroscopy, electrochemistry, atomic force microscopy and density functional theory (DFT) studies.