Two new hybrid polymeric iodoargentates, [Ag2I2(phen)](n) (1; phen = 1,10-phenanthroline) and [AgI(bpt)](n) (2; bpt = 3,5-bis(pyrazinyl)-1,2,4-triazole), were prepared by the hydrothermal methods. 1 displays a new type of taenioid, [Ag2I2(phen)](n), chain incorporating phen molecules, while 2 exhibits a unique 2D hybrid iodoargentate based on a combination of the [AgI](n) layer and bpt molecules as electron acceptors. Such a 2D layer is the first example of an inorganic iodoargentate layer covalently bonding to aromatic N-heterocycle derivatives within the iodoargentates. 1 and 2 exhibit photocurrent response properties.