A novel 1-D organic–inorganic silver(I)-iodide coordination architecture [(C10H16N)3(Ag6I9)]n (1) (C10H16N=N-butyl-2-methyl-pyridinium) templated by appropriate cation has been constructed and structurally and optically characterized. The inorganic moiety of 1 presents one-dimensional hackle chain arrangement that results from the edges-sharing of AgI4 tetrahedrons. Static attracting interactions between organic counter cations and inorganic chains are presented and contribute to the crystal packing. The optical limiting experiment shows that the present polymer exhibits a large optical limiting capacity.