We present evidence for Cp* being a sacrificial placeholder ligand in the [Cp*IrIII(chelate)X] series of homogeneous oxidation catalysts. UV-vis and 1H-NMR profiles as well as MALDI-MS data show a rapid and irreversible loss of the Cp* ligand under reaction conditions, which likely proceeds through an intramolecular inner-sphere oxidation pathway reminiscent of the reductive in-situ elimination of diolefin placeholder ligands in hydrogenation catalysis by [(diene)MI(L,L’)]+ (M = Rh and Ir) precursors. When oxidatively stable chelate ligands are bound to the iridium in addition to the Cp*, the oxidized precursors yield homogenous solutions with a characteristic blue color that remain active in both water- and CH-oxidation catalysis without further induction period. Electrophoresis suggests the presence of well-defined Ir-cations, and EDX, XPS, 17O-NMR, and resonance-Raman spectroscopy data reveal the molecular identity of the blue species to be a bis-µ-oxo di-iridium(IV) coordination compound with two waters and one chelate ligand bound to each metal. DFT calculations give insight into the electronic structure of this catalyst resting state, and time-dependent simulations confirm assignments of the experimental spectroscopic data. [(cod)IrI(chelate)] precursors bearing the same chelate ligands are shown to be equally effective pre-catalysts for both water- and CH-oxidations using NaIO4 as chemical oxidant.