We report on the fabrication of self-assembled monolayers of metal tetraphenyl porphyrins, MTPP, M being CoII or ZnII. The macrocycles were fixed by their metallic center owing to a coordination bond with a pyridine ligand SiPy that was used for the silica substrate silanization. Because of the intense absorption of the MTPPs Soret band, UV-vis spectroscopy could be used to study the macrocycle complexation kinetics. The SiPy/MTPP structure was also characterized step by step with X-ray photoelectron spectroscopy. The present work establishes the possibility to form a self-assembled metalloporphyrin monolayer complexed on a ligand layer.