Acid-base properties of tetra-anionic zinc meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin (ZnTPPS) in presence of cationic and anionic polyelectrolytes are studied by UV-visible spectroscopy. In fact, spectral modifications related to the out-of-plane deformation of porphyrins after protonation allow for an easy probing of the protonation event that, in presence of a metal derivative, requires a deprotonation step. Interactions with poly-D-glutamate and poly-L-lysine, modulated by system electrostatics and by the presence of an axially-coordinated central metal ion, trigger both protonation occurrences as well as porphyrin self-aggregation. The crucial role of electrostatic interactions experienced by the metalated inner core in strong acid solution, probed by UV-visible spectroscopy, are discussed.