We report the single crystal XRD and MicroED structure, magnetic susceptibility, and EPR data of a series of CaMn3IVO4 and YMn3IVO4 complexes as structural and spectroscopic models of the cuboidal subunit of the oxygen‐evolving complex (OEC). The effect of changes in heterometal identity, cluster geometry, and bridging oxo protonation on the spin‐state structure was investigated. In contrast to previous computational models, we show that the spin ground state of CaMn3IVO4 complexes and variants with protonated oxo moieties need not be S=9/2. Desymmetrization of the pseudo‐C3‐symmetric Ca(Y)Mn3IVO4 core leads to a lower S=5/2 spin ground state. The magnitude of the magnetic exchange coupling is attenuated upon oxo protonation, and an S=3/2 spin ground state is observed in CaMn3IVO3(OH). Our studies complement the observation that the interconversion between the low‐spin and high‐spin forms of the S2 state is pH‐dependent, suggesting that the (de)protonation of bridging or terminal oxygen atoms in the OEC may be connected to spin‐state changes.