The interest in the chemistry of cobalt (II) tetrasulfonated phthalocyanine (PcTsCo) comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride) (PAH) in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.