Two new organically templated silver iodides, namely [(bmph)(Ag5I7)]n(1) and [(Hteda)4(Ag12I16)]n(2), have been synthesized with bmph2+and teda [bmph2+= 1,6‐bis(4‐methylpyridinio)hexane, Hteda = protonated triethylenediamine] as structure‐directing agents. Complex 1consists of a one‐dimensional polymer that can be described as edge‐sharing AgI4tetrahedra, whereas 2is the first example of a three‐dimensional Ag/I framework based on Ag···Ag weak interactions and an organic template. Electrostatic interactions between the organic countercations and inorganic moieties are present and contribute to the crystal packing. Both compounds have been further characterized by IR spectroscopy, elemental analysis, TGA, and optical limiting measurements. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)