In our quest to find a suitable photocatalytic system for oxidative con-PET, inspired by the recent work from the Wasielewski lab, 36 we selected triarylamines (Ar 3 N) as potential candidates. Prompted by their ability to form stable radical cations Ar 3 N •+ , which are used as stoichiometric oxidants, we envisaged that excitation of such radicals with visible light could dramatically enhance their oxidation power. Here, we investigated the possibility of the formation of stable Ar 3 N •+ upon irradiation of Ar 3 N in the presence of a terminal oxidant, such as molecular oxygen. Further, we explored if such stable Ar 3 N •+ can subsequently be excited by a second photon to form a potential super-oxidant Ar 3 N •+ * with a redox potential of E ox ≫ +3.0 V vs. SCE that will allow for electron abstraction from a substrate regenerating the neutral form of the photocatalyst, closing the catalytic cycle, and initializing substrate transformation (Figure ).