In this study, we have preserved the hydrated form of Ni electrocatalysts aged under alkaline conditions relevant to the OER. We prepared a series of electrocatalysts with nano- and micro-scale grains that were polished to a similar nano-scale roughness. First, we electrochemically aged Ni electrocatalysts with nanoscale and microscale grains by potential cycling techniques (i.e., cyclic voltammetry). Following electrochemical aging, the Ni electrocatalysts were preserved by immersion in liquid nitrogen and sublimed in a lyophilizer. After this freeze-drying process, the electrocatalysts were imaged under cryogenic conditions using scanning electron microscopy (SEM) techniques. A comparison was made to aged electrocatalysts where freeze-drying was implemented and those that were allowed to air dry. The surfaces of aged Ni electrocatalysts were all observed to contain an electrochemically active layer with a gel-like form. When the catalysts were air-dried, the layer appeared to have a collapsed, web-like texture. Through the use of transmission electron microscopy analyses, it was determined that these gel-like layers contained predominantly nanocrystalline β-phase nickel hydroxide (β-Ni(OH)₂), which likely formed due to relaxation of the OER active beta-phase nickel oxyhydroxide [β-NiOOH] prior to the imaging process. The formation of the gel-like layer covering these electrocatalysts has implications for dynamic processes taking place at their interface with the electrolyte. Processes influenced by the gel-like form of this active layer include the rates of diffusion of electrolyte, the mechanism of O₂ bubble nucleation, and the mechanics of bubble release. The results of these studies also have implications for the electrocatalytic activity and stability of other types of electrocatalysts. Further, this work can be extended for the design of new electrocatalysts for a variety of electrocatalytic processes, such as the hydrogen evolution reaction and other gas evolution reactions.