Traditional understanding of electrocatalytic reactions generally focuses on either covalent interactions between adsorbates and the reaction interface (i.e., electrical double layer, EDL) or electrostatic interactions between electrolyte ions. Here, our work provides valuable insights into interfacial structure and ionic interactions during alkaline oxygen evolution reaction (OER). The importance of inner-sphere OH^- adsorption is demonstrated as the IrO_x activity in 4.0 M KOH is 6.5 times higher than that in 0.1 M KOH. Adding NaNO₃ as a supporting electrolyte, which is found to be inert for long-term stability, complicates the electrocatalytic reaction in a half cell. The nonspecially adsorbed Na⁺ in the outer compact interfacial layer is suggested to form a stronger noncovalent interaction with OH^- through hydrogen bond than adsorbed K⁺, leading to the decrease of interfacial OH^- mobility. This hypothesis highlights the importance of outer-sphere adsorption for the OER, which is generally recognized as a pure inner-sphere process. Meanwhile, based on our experimental observations, the pseudocapacitive behavior of solid-state redox might be more reliable in quantifying active sites for OER than that measured from the conventional EDL charging capacitive process. The interfacial oxygen transport is observed to improve with increasing electrolyte conductivity, ascribing to the increased accessible active sites. The durability results in a liquid alkaline electrolyzer which shows that adding NaNO₃ into KOH solution leads to additional degradation of OER activity and long-term stability. These findings provide an improved understanding of the mechanistic details and structural motifs required for efficient and robust electrocatalysis.