Water electrolysis remains the most promising pathway towards the sustainable provisioning of H₂ at the terawatt scale. Unfortunately, a competitive hydrogen pricing against that derived from fossil fuels remains limited by the capital and ongoing expenditures of current state-of-the-art water electrolyser technologies. It is therefore necessary for future sustainable hydrogen economies that the development of noble-metal-free electromaterials be made to withstand the harsh electrolytic conditions imposed by efficient proton exchange membrane water electrolysis (PEMWE). However, the advancement of cost-effective anode catalysts for industrially relevant PEMWE has thus far been infrequent and relatively unsuccessful. Of the trivial sum of sufficiently stable modes of the oxygen evolution reaction (OER) within low-pH electrolytes, self-healing systems demonstrate a potential towards earth-abundant OER under industrially relevant PEMWE conditions. Self-healing mechanisms are defined by a quasi-equilibrated state between surface and dissolved catalytic components, whether added intentionally or corroded from the catalyst itself, and can therefore provide a perceptible means for long-lifetime electrolytic operation. From this perspective, detailing such a mode of electrocatalysis proves highly useful within a range of electrolytic applications including but not limited to water oxidation, as a large sum of electromaterials and electrochemical pathways often rely on the equilibration between surface and dissolved electroactive species. Here at Monash University, Swinburne University of Technology and Max-Planck-Institut for Chemical Energy Conversion, operando X-ray spectroscopic and voltammetric techniques have been developed in order to track a self-healing water oxidation mechanism.^1-2 Using a highly stable and high performance Co-based OER catalyst within low-pH conditions,³ utilisation of in situ Co K and L₃-edge X-ray absorption spectroscopy (XAS) in conjunction with electrochemical Quartz Crystal Microbalance (eQCM) and Fourier Transformed alternating current Voltammetry (FTacV) has allowed the successful tracking of the oxidative changes within the catalysts electronic structure. From a predominant Co(II) ground state to its catalytically relevant Co(III) oxidative structure under operation, the charge- and mass-transfer processes have also been compared against the redox events occurring during the self-healing OER mechanism, providing in detail, the potentials at which both the electron- and mass-transfers begin and the effect of catalytic loading on cobalt selective process. Further details of the mechanistic insights into both static and dynamic electro- and spectroelectrochemical techniques will be elaborated on through both poster submission and oral presentation.