Two silver/azide/organodiimine adducts have been isolated and characterized as supramolecular coordination polymers (SCP); [AgN3·L] where L = 4,4′-bipyridine, 1, trans-1,2-bis(4-pyridyl)ethylene, 2. The syntheses were carried out in H2O/CH3CN/NH3 media at room temperature. The topology of the bipodal ligands directs the silver azide building blocks to adopt different 1D-chains as the size and length of the bipodal ligand is increased. The Ag(1) atom in 1 and 2 forms distorted square planar configuration. The emission spectra of 1 and 2 display structural emission peaks at 400–650 nm.