The syntheses and crystal structures of novel supramolecular coordination polymers (SCPs) of AgCN with bipodal ligands; 4,4′-bipyridine (bpy), trans-1,2-bis(4-pyridyl)ethylene (tbpe) and 1,2-bis(4-pyridyl)ethane (bpe) are reported. The syntheses were affected in H 2 O/acetonitrile/NH 3 media at room temperature. SCP [(AgCN) 2 ·bpy] (1) is monoclinic and crystallizes in the space group P2 1 /c, a=9.0565(4)Å, b=16.0063(8)Å, c=9.1361(4)Å, β=110.51° and Z=4. SCP [(AgCN) 3 ·(tbpe) 2 ·H 2 O] (2) is triclinic and crystallizes in the space group P1¯, a=9.8427(4)Å, b=10.3596(4)Å, c=14.0864(6) Å, α=98.873°, β=101.739°, γ=95.506° and Z=2. SCP [(AgCN) 4 ·bpe] (3) is monoclinic and crystallizes in the space group P2 1 /c, a=10.1872(5) Å, b=9.1610(5) Å, c=14.4862(6) Å, β=130.00(18)° and Z=2. The 3D-topolgies of 1–3 resulted from the bridging action of the bipodal ligands and the argentophilic interactions as well as extensive H-bonding and π–π stacking.