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Miniaturized sensors possess many advantages, such as rapid response, easy chip integration, a possible lower concentration of target compound detection, etc. However, a major issue reported is a low signal response. In this study, a catalyst, the atomic gold clusters of Au_n where n = 2, was decorated at a platinum/polyaniline (Pt/PANI) working electrode to enhance the sensitivity of butanol isomers gas measurement. Isomer quantification is challenging because this compound has the same chemical formula and molar mass. Furthermore, to create a tiny sensor, a microliter of room-temperature ionic liquid was used as an electrolyte. The combination of the Au₂ clusters decorated Pt/PANI and room temperature ionic liquid with several fixed electrochemical potentials was explored to obtain a high solubility of each analyte. According to the results, the presence of Au₂ clusters increased the current density due to electrocatalytic activity compared to the electrode without Au₂ clusters. In addition, the Au₂ clusters on the modified electrode had a more linear concentration dependency trend than the modified electrode without atomic gold clusters. Finally, the separation among butanol isomers was enhanced using different combination of room-temperature ionic liquids and fixed potentials.