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We report the synthesis and ion-binding properties of four poly(crown-ethers) displaying either one or two crownethers (15-crown-5 or 18-crown-6) on every third carbon alongside the backbone. The polymers were synthesized by living anionic ring-opening polymerization of disubstituted cyclopropane-1,1-dicarboxylates monomers. Cation binding of the polychelating polymers and corresponding monomers to Na 1 and K 1 was evaluated by picrate extraction and isothermal calorimetry titra-tion. This novel family of poly(crown-ethers) demonstrated excellent initial binding of the alkali ions to the polymers, with a higher selectivity for potassium.