Ionspray mass spectrometry (MS) of a water-acetonitrile solution of 1:1 γ-cyclodextrin (γCD)/12-crown-4 ether (12-C-4) double macrocyclic inclusion complex added with LiBr and ammonium acetate allowed the detection of 1:1:1 γCD/12-C-4/Li + or NH 4 + gaseous associations, which were characterized by tandem-MS experiments performed with a triple quadrupole analyser. The low energy collision-induced dissociation (CID) products were both γCD and 12-C-4 cationated with Li + or NH 4 + , respectively. The CID of 1:1:1 γCD/12-C-4/NH 4 + also yielded protonated γCD and 12-C-4. Li + or NH 4 + cationated γCD were more abundant than the corresponding cationated 12-C-4. These results suggested preferential cationization of γCD at the external hydrophilic surface with respect to 12-C-4 cation inclusion within the 1:1 double macrocyclic complex for entropy and steric hindrance reasons. Nevertheless, the 12-C-4 cationization did yet even occur to a significant extent, thus providing support for the surviving capability of a cationated gaseous CD host-guest complex with the charge located within the host cavity.