The complexation and ion-association behavior of acyclic polyethers having anthraquinone terminal groups in acetonitrile are studied with chromatography-voltammetry. Polydispersed acyclic polyethers are separated into monodispersed components with chromatography according to their complexation ability with ammonium ions anchored on the silica gel surface; separation of polyethers gives the information on the complexation of electrically neutral (unreduced) polyethers. After chromatographic separation, monodispersed components are fed into a voltammetric cell, where cyclic voltammetric studies are carried out to obtain the information on the interaction between metal ions and polyethers having anion-radical terminals. Their interaction constants are determined based on the measurements of reduction currents. The comparison of the ion-association constants of anion radicals with the complexation constants of the neutral polyethers allows us to infer the differences in structures between Li+- and Na+-anion radical ion-associates.