The effect of acidic gases present in flue gas, specifically NO, on the capture of CO 2 by the superbase ionic liquid, trihexyltetradecylphosphonium benzimidazolide ([P 66614 ][Benzim]), is reported. An online mass spectrometry technique was utilized to study the CO 2 uptake of the ionic liquid during multiple absorption and desorption cycles of a gas feed containing NO and CO 2 at realistic flue gas concentrations, and it was found that while NO alone could bind irreversibly, the CO 2 capacity of the IL was largely unaffected by the presence of NO in a co-feed of the gases. In-situ attenuated total reflection (ATR) infrared was employed to probe the competitive absorption of CO 2 and NO by [P 66614 ][Benzim], in which carbamate and NONOate species were observed to co-bind to different sites of the benzimidazolide anion. These effects were further characterised by analysing changes in physical properties (viscosity and nitrogen content) and other spectroscopic changes (1 H NMR, 13 C NMR and XPS). Density functional theory (DFT) computations were used to calculate binding energies and infrared frequencies of the absorption products, which were shown to corroborate the results and explain the reaction pathways.