Polymer electrolyte membrane water electrolyzers (PEMWEs) offer greenhouse gas emission-free hydrogen production for fuel cell vehicles and other industrial uses when using renewable energy sources [1]. Unsupported iridium oxide (IrO2) is the most active stable oxygen evolution reaction (OER) catalyst utilized in the anode of the PEMWE [2]. The atomic and microstructure of IrO2 catalysts and electrodes and interactions between and ionomer and catalyst can affect the ultimate performance of the PEMWE anode. These properties and phenomena may be controlled by the interactions of the ionomer in the catalyst-ionomer ink, by the effect of ink solvent composition on those interactions, and by the ink mixing and coating procedures. The microstructure evolution of the IrO2 catalyst during ink processing has not yet been identified. This presentation will describe relationships between ink formulation, electrode morphology, and performance for the IrO2-based PEMWE anodes. Moreover, the results of the evolution of the catalyst layer during the ink drying process as a function of solvent removal rate and solvent identity will be discussed. This study uses the in-situ technique of ultra-small angle X-ray scattering (USAXS) combined with small angle X-ray scattering to determine particle size distributions and the extent of IrO2 agglomeration in the inks and electrodes during the ink mixing/settling and drying processing. The effects of ionomer concentration, catalyst concentration, and solvent composition on the microstructure of the catalyst inks and electrode are correlated with the PEMWE performance and operando diagnostic data. Acknowledgements This work was supported by the U.S. Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office under the H2NEW Consortium. This work was authored in Argonne National Laboratory, a U.S. Department of Energy (DOE) Office of Science laboratory operated for DOE by UChicago Argonne, LLC under contract no. DE-AC02-06CH11357. This research used the resources of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.