In this work, CO adsorption and oxidation processes were studied with cyclic voltammetry and anodic adsorptive stripping chronoamperometry in two structural different ionic liquids (ILs) (i.e., 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Bmpy] [NTf2] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][NTf2]). Multiple redox processes were observed in the ILs. During the anodic oxidation processes, the NTf2- anion is oxidized to form NTf2 center dot radical and CO is oxidized to CO2 and produces a proton in these ILs when a trace amount of water is present. The products of oxidation processes (NTf2 center dot radical and proton) can be reduced at cathodic processes. Results show that the cation in these ILs can facilitate the formation of an electrolyte-electrode interface structure that influences the amount of CO adsorbed as well as the subsequent CO oxidation current and charge. By selecting the anodic and cathodic potentials, we developed an innovative electroanalytical method for CO sensing based on a simple double-potential adsorptive stripping chronoamperometry. The method allows calibration of the concurrent NTf2- anion and CO redox processes as well as the double-layer charging and discharging processes in the IL with the presence of a trace amount of water providing quantitative analysis of CO concentration with high accuracy and sensitivity. The reported method is the first work to show that quantitative CO detection can be achieved in the presence of complex dynamic interfacial processes in the ILs. The trace water present in the ILs is beneficial for CO oxidation, but a large amount of water is detrimental for the CO oxidation in ambient condition.