As part of a mass spectrometric investigation of the binding properties of sulfonamide anion receptors, an atmospheric pressure chemical ionization mass spectrometric (APCI-MS) method involving direct infusion followed by thermal desorption was employed for identification of anionic supramolecular complexes in dichloromethane (CH2Cl2). Specifically, the dansylamide derivative of tris(2-aminoethyl)amine (tren) (1), the chiral 1,3-benzenesulfonamide derivatives of (1R,2S)-(+)-cis-1-amino-2-indanol (2), and (R)-(+)-bornylamine, (3), were shown to bind halide and nitrate ions in the presence of (n-Bu)4N+X- (X- = Cl-, NO3-, Br-, I-). Solutions of receptors and anions in CH2Cl2 were combined to form the anionic supramolecular complexes, which were subsequently introduced into the mass spectrometer via direct infusion followed by thermal desorption. The anionic supramolecular complexes [M + X]-, (M = 1-3, X- = Cl-, NO3-, Br-, I-) were observed in negative mode APCI-MS along with the deprotonated receptors [M - H]-. Full ionization energy of the APCI corona pin (4.5 kV) was necessary for obtaining mass spectra with the best signal-to-noise ratios.