Photoredox catalysis employing metal-based as well as organic photocatalysts has developed into a modern, powerful toolbox for synthetic organic chemistry. The direct oxidative functionalization of benzene and its derivatives to replace the C-H bond by a C-N bond is a challenging and synthetically highly useful reaction. It represents a short-cut to the widely utilized Buchwald-Hartwig amination which requires pre-functionalized starting materials and transition metal catalysts. Nicewicz and co-workers developed the oxidative amination of electron-rich arenes utilizing acridinium based photocatalysts in combination with oxygen and TEMPO as an additional additive (Scheme 1A). Initially, the transformation was limited to electron-rich arenes such as anisole but was not performed with benzene or electron-deficient derivatives, since the oxidation potentials are too high. To access such high oxidation potentials other concepts are required (Scheme 1B). Wickens and co-workers developed arene azolation reactions using an organic photocatalyst utilizing the consecutive Photoinduced Electron Transfer (conPET) mechanism, which was also exploited by Wagenknecht for challenging oxidations. The method was effective for benzene or methylated arenes, whereas the oxidation of electrondeficient arenes, such as PhCl, produced a low yield of only 22% of the azolated product. An alternative to the conPET process has been recently reported by the Lambert and Barham groups using a photo electrocatalytic approach. However, this method requires specific, additional electrochemical equipment and is technically more complex compared to Nicewicz's arene amination involving a purely photochemical process. Without electrochemical conditions, no products or a very low yield were observed and in general very long reaction times were required. Thus, promoting this transformation using photochemical strategies would be a synthetically convenient addition to existing processes. The aim of developing a photocatalyst system that can efficiently oxidize feedstock aromatic compounds like benzene, as well as electron-deficient arenes, through a single photoexcitation remains an exciting challenge. To achieve strongly oxidative redox potentials, new photocatalyst design concepts are highly desired, especially since organic chromophores offer plenty of space for structural design. In contrast to more sophisticated conPET and photo electro chemistry concepts, we envisioned the modification of the well-known Fukuzumi catalyst I (Figure ). While there have been modifications to the Fukuzumi catalyst, those structural changes typically relate to rather minor changes of the acridinium core in order to increase the photochemical stability (Nicewicz's catalysts II). Here, we present a strong modification exchanging the mesityl fragment with a cationic heterocycle. Note, this exchange is not trivial since the mesityl group plays a crucial role in accessing the long-lived charge-transfer Acr • -Mes •+ state. The idea was to access highly electron-deficient catalysts in the ground-state based upon dications thereby raising the ground-state oxidation potential. When excited by a single photon, they should become a powerful photocatalyst for oxidative photocatalysis, bypassing conPET and photo electro mechanisms (Figure ). Here we describe the photocatalyst synthesis, application and photochemical characterization including mechanistic studies of a dicationic photocatalyst design.