The immobilisation of [15]aneNO 4 , [15]aneN 2 O 3 , and [18]aneN 2 O 4 onto the oxirane and thiirane containing copolymers p(GMA-O) and p(GMA-S) resulted in six aza crown ether containing polymers with interesting metal-ion affinities. The pendent hydroxy or thiol groups, originating from the polymeric backbones, appeared to play an important role in the observed metal-ion affinities. The metal-ion affinity of p(GMA-O)-[15]aneN 2 O 3 for a range of cations was found to decrease with decreasing ionic radius: Ag + Ͼ Pb 2+ Ͼ Cd 2+ Ͼ Cu 2+ . The thiol-containing analogue of this polymer, p(GMA-S)-[15]aneN 2 O 3 , showed a reversed Cd 2+ /Cu 2+ selectivity. This illustrates the capability of pendent hydroxy groups to