The association of pentammine ruthenium(II) with the reducible ligand 44’azopyridine leads to a pH induced redox reaction in which ruthenium is oxidized to the III state, while 44’azopyridine is reduced to hydrazopyridine. In this process, the conjugated ligand is transformed in a nonconjugated one, with loss of its intramolecular electron transfer properties. In order to exploit thiscontrol of an intramolecularelectron transfer by a protonation process, we have prepared ‘‘shish‐kebab’’ polymers by first inserting ruthenium in tetrakis (3,5‐diterbutyl 4‐hydroxyphenyl) porphyrin under a CO atmosphere. The resulting Ru(CO)porphyrin complex is photochemically decarbonylated in the presence of bridging ligands (44×azopyridine or pyrazine). Polymers are thus obtained, which can be oxidized by iodine, giving rise to intervalence transitions between ruthenium(II) and (III) in the near‐infrared. This provides a convenient way to monitor electron transfer along the polymer chain. In the case of 44’azopyridine, the pH induced redox reaction is again observed. Starting from a homovalent ruthenium(II) chain, this gives the possibility to switch ‘‘ON’’ or ‘‘OFF’’ the intervalence transition by a protonation/deprotonation reaction.