Type I photostable photosensitizing assemblies of DPZ-TPY have been developed using phenazine as a strong acceptor and terpyridine groups as a weak acceptor. The as-prepared DPZ-TPY assemblies exhibit sufficient excited state potential to catalyse the synthesis of symmetrical azoaromatics through direct regulated oxidation of anilines in excellent yields (93%), without the formation of over-oxidized product. Consequently, DPZ-TPY assemblies also catalyse the formation of unsymmetrical azoaromatics starting from hydrazobenzenes under mild reaction conditions. The potential of DPZ-TPY assemblies to catalyse the gram-scale synthesis of azobenzene demonstrates their real-time application.