The reaction of 2,5,8-trithia[9]-m-cyclophane (L(1)) with AgCF3SO3 in a 1:1 ratio produced the polymeric material {[Ag(L(1))][CF3SO3]. CH3CN}(x). This polymer crystallized in the space group P2(1)/c with a = 11.218(2) Angstrom, b = 11.317(3) Angstrom c = 17.035(7) Angstrom, beta = 104.17(2)degrees, V = 2097(2) Angstrom(3), and Z = 4. The structure refined to R = 4.11% and R(W) = 5.69% for 1261 reflections with F-o(2) > 3 sigma(F-o(2)). NMR solution data indicate a multiplicity of solution structures in rapid exchange. The exchange of L(1) and analogues with their respective silver complexes in CD3CN/CD2Cl2 was examined by NMR spectroscopy. The L(1) exchange on silver was shown by the dilution method to be D or I-D in character.