The cyclopolymerizations of 2,6-bis[7’-(4 "-ethynylphenoxy)-2’,5’-dioxaheptyl]pyridine (1a) and 2,6-bis[10’-(4 "-ethynylphenoxy)-2’,5’,8’-trioxadecyl]pyridine (1b) were carried out using the (bicyclo[2.2.1]-hepta-2,5-diene)rhodium(I) chloride dimer. The yellowish powdery, organic solvent-soluble polymers were obtained using an amine as a cocatalyst. The resulting polymers consisted of cyclic constitutional repeating units as the main structure along with pendant acetylenic groups, i.e. the extent of cyclization was from 0.89 to 0.99 for the polyphenylacetylenes with an azacrown cavity, 2a and 2b, obtained from monomers la and Ib, respectively. Polymer 2 exhibited cation-binding ability for alkaline earth metal, heavy metal, and transition metal ions and, in particular, for Ag+. The complex of 2 with Ag+, which was confirmed by the H-1 n.m.r. spectrum, consisted of the azacrown cavity and Ag+ with a ratio of 2.