Oxygen reduction and ethanol oxidation reactions were studied on Au(1 11), Pt(1 1 1) and Ir(1 1 1) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (1 1 1) surface orientation and exploring oxophilicity trends and non-covalent interactions between OHad and alkali metal cations (AMC(n+)), we were able to gain deep insights into the multiple roles that OHad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OHad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OHad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formation of a "true oxide" layer at higher electrode potentials. Although OHad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li+) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na+, without changing the product distribution for the reaction. This cation effect suggests that OHad-Li+(H2O)(x) clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction. (C) 2015 Elsevier B.V. All rights reserved.