The self-organization of bis-cyclodextrinyl-lariats (CD-L's) around divalent metal-sulfonates is described. Several new pseudo-rotaxanes were prepared by a template-directed approach involving bis-CD-L synthetic receptors and bis-sulfanilate or bis-tosylate metal salts as anion/cation guests. The non-covalent interactions between hosts and Zn^II, Cu^II, Ca^II bis-arylsulfonates guests were studied by 1D- and 2D-NMR confirming the formation of 1 : 1-complexes driven by a dual anion/cation recognition.