Our results suggest that the ability of the Chl D1 Pheo D1 pair to create a charge separated species is much greater than of the P D1 P D2 pair. Intriguingly, the Chl D1 Pheo D1 pair exhibits a uniform distribution of Chl D1 →Pheo D1 CT character over the entire visible spectrum. Moreover, the lowest lying excited state is a CT state, which suggests a possible stabilization of the charge separated species after vibrational cooling and internal conversion. In contrast, CT character is only found at the high energy end of the visible spectrum of the P D1 P D2 pair. Internal conversion after an excitation would thus produce only locally excited states. The present results therefore provide independent support to the mechanistic scenario where the Chl D1 Pheo D1 pair is the actual "special pair" for the primary charge separation in PSII. This conclusion contrasts with interpretations proposed in some experimental studies that favor initial charge separation within the P D1 P D2 pair or implicate Chl D1 as acceptor, but is aligned with the intepretations reached by several other studies, as well as with recent multiscale theoretical investigations of the RC. In terms of future perspectives, we note that our results can be used to parameterize model exciton Hamiltonians for open quantum system simulations to reconstruct time-resolved or twodimensional spectra, an approach that would complement other recent efforts in this direction. Most importantly, the approach demonstrated here for the charge-separating pigment assembly of oxygenic photosynthesis can be applied directly to synthetic systems, leading to a deeper understanding of the structural factors -and, hence, identification of design principles-that control the initiation of electron transfer cascades in natural and artificial photosynthesis.