Polymer-electrolyte fuel cells and electrolyzers (PEFC&Es) have the potential to play a prominent role in green energy technologies including transportation, chemical manufacturing, and grid-scale energy storage. PEFC&Es have made significant advancements in recent years, largely due to improvements in the catalyst layers, and especially at the ionomer/catalyst interface. However, it is not yet definitively known how this solid-state environment impacts electrochemical kinetics, especially under various operating conditions (e.g., temperature, humidity, etc.). Additionally, it is challenging to probe local conditions at the catalyst/ionomer interface using traditional analytical techniques. In this study, we explore the influence and nature of proton activity in Nafion and 3M ionomers using a specialized microelectrode setup containing a 50 μm platinum microelectrode in a solid-state three-electrode cell for hydrogen oxidation and evolution (HOR&HER) reactions. Proton activity was calculated through open circuit voltage measurements, and was found to increase with increasing water content, mirroring trends in reaction performance. The effect of proton activity on the reactions' kinetics was investigated using semi-empirical fitting with the Butler-Volmer equation, which gives insight into the reaction rate order and possible mechanism for the reactions. This study demonstrates that microelectrodes can be used to probe solid-state kinetics and can also elucidate complex ion interactions within the ionomer at the catalyst/ionomer interface.