We present the fabrication and use of a film of a carborane-thiol-protected tetranuclear copper cluster with characteristic orange luminescence using ambient electrospray deposition (ESD). Charged microdroplets of the clusters produced by an electrospray tip deposit the clusters at an air-water interface to form a film. Different microscopic and spectroscopic techniques characterized the porous surface structure of the film. Visible and rapid quenching of the emission of the film upon exposure to 2-nitrotoluene (2-NT) vapours under ambient conditions was observed. Density functional theory (DFT) calculations established the favourable binding sites of 2-NT with the cluster. Desorption of 2-NT upon heating recovered the original luminescence, demonstrating the reusability of the sensor. Stable emission upon exposure to different organic solvents and its quenching upon exposure to 2,4-dinitrotoluene and picric acid showed selectivity of the film to nitroaromatic species.