This communication demonstrates the effect of electrostatically adsorbed alkali cations at electrochemical interface towards methanol oxidation reaction (MOR) in acidic medium. The well-known electrostatic interaction between adsorbed OH/(OHad) species of catalyst surface and hydrated metal cations (M+(H2O)(x)) at the interface could be accountable for the observed different electrocatalytic activity of Pt/C and f-MWCNT/Pt-Co alloy NPs towards MOR. This cation effect has been found predominantly in weekly adsorbed ClO4- ion at Pt/C and f-MWCNT/Pt-Co alloy NPs surface than that of strongly adsorbed SO42- ion. Cyclic voltammetry results reveal that the strongly adsorbed cation at the interface shifts the oxidation potential more positively than that of weekly adsorbed cation.