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Photosystem‐II (PSII) is a multi‐subunit protein complex that harvests sunlight to perform oxygenic photosynthesis. Initial light‐activated charge separation takes place at a reaction centre consisting of four chlorophylls and two pheophytins. Understanding the processes following light excitation remains elusive due to spectral congestion, the ultrafast nature, and multi‐component behaviour of the charge‐separation process. Here, using advanced computational multiscale approaches which take into account the large‐scale configurational flexibility of the system, we identify two possible primary pathways to radical‐pair formation that differ by three orders of magnitude in their kinetics. The fast (short‐range) pathway is dominant, but the existence of an alternative slow (long‐range) charge‐separation pathway hints at the evolution of redundancy that may serve other purposes, adaptive or protective, related to formation of the unique oxidative species that drives water oxidation in PSII. [ABSTRACT FROM AUTHOR]