We set out to investigate methyl viologen as a suitable electron-poor acceptor for EDA complexation with different electron donors for application in synthesis. Herein, we explore methyl viologen in catalytic amounts for the photoinduction of formal [2+2] and [4+2] photocycloadditions via EDA complexes. As our target reaction we selected the radical cationic cyclization reaction between anethole and isoprene to form the desired cyclohexenes. In order to enable the desired reactivity, we propose the formation of a charge transfer complex between the electron-rich anethole and the electron-poor methyl viologen, followed by radical addition of the anethole radical cation to isoprene. Therefore, we conducted UV/Vis-studies of this pair in different solvents. In these studies (Figure ), we observed the formation of charge transfer bands in trifluoroethanol (TFE), aqueous sodium dodecyl sulfate (SDS) solution and methanol. The formation of the EDA complex was more pronounced in the aqueous micellar solution compared to the organic solvents. This is likely due to the increased local concentration in the aqueous micellar solution leading to a stronger signal for the EDA complexation. Preliminary studies show that no product formation was observed in the aqueous SDS solution (details available in SI). However, in TFE the desired product was observed, allowing us to investigate the formal [4+2] cycloaddition. All UV/Vis spectra exhibited absorption around λmax = 450 nm which could relate to the predicted absorption of the methyl viologen radical cation MV•+.20 To confirm this hypothesis, a spectroelectrochemical measurement of methyl viologen in TFE was conducted (Figure ) and as the reduction potential decreased, an absorption band emerged around λmax = 450 nm. The single reduced methyl viologen correlates to the signal observed in the UV/vis spectra of the mixture of anethole and methyl viologen. Consequently, the presence of this absorption band correlates with the formation of the MV•+.