Crown ether decorated phthalocyanines were designed to form rigidly eclipsed aggregates with metal ions being sandwiched between the molecules. We studied tetra[18]crown-6 ether functionalized zinc phthalocyanine (ZnPcTetCr) in the presence of excess NaC1 by electrospray ionization mass spectrometry. ZnPcTetCr was found to form aggregates in the gas phase to which several neutral NaCI molecules are attached. Collision-induced dissociation experiments revealed that the ions observed in the positive- and negative-ion modes possess remarkably different structures. Their fragmentation behavior indicates that the sodium ions providing the charge of the positively charged aggregates are strongly bound inside the crown ether moieties, while the neutral salt units are less strongly attached. However, in the negatively charged ions, none of the sodium ions is embedded in the crown ether moieties, and the NaCl molecules were found to be attached as one large, weakly bound cluster.