Low-temperature polymer electrolyte membrane water electrolyzers (PEMWE) are an attractive clean energy technology to produce hydrogen (H₂), which is an energy carrier for several applications such as transportation and grid-scale energy storage and distribution (as supported by the US Department of Energy’s H2@Scale initiative). The catalyst layers -- composed of catalyst particles and ionomer, which acts as a binder for the catalyst and a proton conducting medium -- are key components of the PEMWE membrane electrode assembly (MEA). The catalyst layers are commonly fabricated by solution-processing an ink, which is a mixture of catalyst and ionomer often dispersed in a water-alcohol solvent mixture. Tuning the rheological properties of the anode inks (typically composed of iridium oxide catalyst, IrOx), particularly increasing their viscosity without significantly increasing the solids loading, to suit various scalable coating methods, is generally a challenge due to relatively low porosity and high density of the IrOx catalysts compared to the carbon-supported cathode catalysts. The typically low viscosities of the anode inks combined with high particle densities often cause stability/settling issues and challenges obtaining unform coatings, leading to inhomogeneous distribution of the catalyst that may have a negative effect on electrode performance. In this presentation we report on a dramatic enhancement in the viscoelasticity of the anode inks with aging, where the ink transitions from a liquid-like to a weak gel-like structure. The steady-shear and oscillatory shear rheology characterizations of the inks as a function of aging/time, the impact of formulation conditions (ionomer-to-catalyst ratio and dispersion media composition) on the viscoelastic enhancement with aging, and possible mechanisms for the observed behavior will be discussed. In addition to the rheological measurements, X-ray scattering characterization of the ink structure will be presented. The implications of the rheological changes on ink stability and processing will also be discussed. Additionally the impact of ink age on MEA performance will be presented.