A series of Na+, Ca2+, and La3+ complexes with octadentate cyclen ligand were prepared and structurally characterized in the crystal and solution states. The employed cyclen ligand formed 6-, 7-, and 9-coordinated, crystalline complexes with Na+, Ca2+, and La3+ cations, respectively, in which the parent cyclen ring and quinoline-functionalized side arms were cooperatively coordinated These three metal cations provided the quadruple-stranded helicates in CH3CN-C2H5OH solutions In each helicate, four quinoline-functionalized side arms were arranged in a propeller-like fashion to yield an enantiomer-pair of Delta- and Lambda- forms. Addition of a chiral anion to the cyclen-Ca2+ complex solution induced circular dichroism (CD) signals around the quinoline chromophore, which indicated that 1: 1 diastereomeric complexation between the Ca2+ complex and the chiral anion imposed the stereoisomeric equilibrium. The intensity and sign of the observed CID signal were significantly dependent on both the absolute configuration and the enantiomeric purity of the added anion. The corresponding cyclen-Na+ complex rarely induced a CD signal, while the La3+ complex exhibited complicated anion-induced spectral changes. Thus, the octadentate cyclen ligand employed was demonstrated to form the quadruple-stranded helicate with the Ca2+ cation in the solution state, which functioned as an effective CD probe for the determination of enantiomer excess (ee%) of the chiral anions.