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The gas-phase affinities of different types of anions X- (halogen anions, oxoanions, and hydrogenated anions) toward a model tetralactam-based macrocycle receptor (1), defined in terms of stability of an anion-receptor complex (1 + X-) against its disintegration, were evaluated by dissociation studies using a mass spectrometry-based methodology and supported by theoretical calculations (density functional theory-PBE. The gas-phase complex with Cl- was found to be tailor-made for the macrocycle 1, while 1 + SA- (SA- = salicylate anion)