Nature's ability to split water into oxygen and protons lies at the heart of oxygenic photosynthesis. Solar energy is absorbed, leading to the excitation of the lowest energy states of the reaction centre of Photosystem II (PSII). Rapid charge separation of the enigmatic entity P680, leads to the formation of P680⁺. This highly oxidative photogenerated state enables, in an intricate, four-photon, four-electron, ratchet-like process to drive the oxidation of two molecules of water to molecular oxygen and four protons at the manganese cluster of PSII. P680⁺ has the highest oxidative potential in all biology and derives its name from the transient bleach at 680 nm seen upon short pulse excitation of PSII. This state has long been held to be the lowest energy state of the reaction centre. We have made the remarkable discovery that the lowest energy optically accessible state of PSII is a weaker, broader transition of an unexpected electronic state at 730 nm. This state has distinctly different properties to the state at 680 nm and is assigned as having charge transfer, rather than dominantly chlorophyll Q band character. The properties of this state are discussed in relation to the overall process of water splitting.