As a complement to the study of 9,10- and 1,4-anthracenocryptands, 2,3-anthraceno[2.2.2]cryptand (1) was synthesized in order to examine the mutual influence of the two components: the cation-binding subunit and the pendent aromatic moiety. It was shown that the receptor subunit induces small perturbations to the absorption spectrum and the fine structure fluorescence spectrum of 1 that are typical of those of 2,3-disubstituted anthracene reference molecules. Conversely, the stability constants towards metal cations (Ks), determined from the electronic spectra using the LETAGROP programme, were found to be altered by the incorporated aromatic component, namely lowered by several orders of magnitude compared with those of [2.2.2]cryptand. For instance, logKs values in CH3CN for 1 were found to be: K+(8); Tl+(10); for [2.2.2]cryptand: K+(11); Tl+(12). The observed decrease of binding ability can be attributed to a relative lack of flexibility of the receptor and some hindrance to cation solvation due to the aromatic component.