Oxygen-evolving complex (Mn4Ca cluster) of Photosystem II cycles through five intermediate states (Si-states, i = 0-4) before a molecule of dioxygen is released. During the Sstate transitions, electrons are extracted from the OEC, either from Mn or alternatively from an oxo ligand. The oxidation state of Mn is widely accepted as Mn4(III2,IV2) and Mn4(III,IV3) for S1 and S2 states, while it is still controversial for the S0 and S3 states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn4Ca complex in the OEC. The RIXS data yield two- dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge (charge density sensitive) and L-edge-like spectra (metal spin state sensitive) simultaneously. The spectral changes in the Mn 1s2p3/2 RIXS spectra between the S-states were compared to those of the Mn oxides and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S0 to S1, and S1 to S2 transitions is twice as large as that during the S2 to S3 transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms. Show Partial Abstract