We present a method to identify and quantify methane using a hydrophobic ionic liquid (IL)-electrified metal electrode interface by electrochemical impedance spectroscopy. We investigated the mechanisms of the responses of the EL-electrified electrode interface to the exposure of methane and other interfering gases (H-2, C6H12, SO2, NO, NO2, CO2, O-2, H2O). Our results show that at low frequency the IL-electrified electrode interface shows a predominantly capacitive response. The IL-electrode double layer (EDL) was found to be the primary response layer while the transition zone and bulk region of the IL-electrode interface contribute little to the overall signal change. For recognition and quantification of methane using the Langmuir adsorption model and measurement of differential capacitance change, an optimum EDL interface structure was found to form at a specific DC bias potential. The cumulative results shown in this work suggest that an ideal IL-electrode interface can be formed by varying IL structure and applied DC bias electrode potential for a specific analyte and that the semi-ordered structure of IL-electrified interface can act as a recognition element for the sensitive and selective adsorption and detection of gaseous molecules. (C) 2013 The Electrochemical Society. All rights reserved.