Two metal-organic coordination polymers, {Co(bbbi)(0.5)(bm)(Hbtc)} (n) (1) and {Ag-2(bbbi)(2)(ntp)(H2O)center dot 4H(2)O} (n) (2), [bbbi = 1,1-(1,4-butanediyl)bis-1H-benzimidazole, bm = benzimidazole, H(3)btc = 1,2,4-trimellitic acid, and H(2)ntp = 2-nitroterephthalic acid], have been hydrothermally synthesized and characterized by physico-chemical and spectroscopic methods and single-crystal diffraction. 1 Features a 1D ladder-like chain and is further connected by O-H center dot center dot center dot O hydrogen bonding interactions to yield a 3D supramolecular architecture. 2 Possesses a 1D infinite zigzag chain connected by bbbi ligands in bis-monodentate mode, which is further extended into a 3D complicated supramolecular network by face-to-face pi-pi stacking interactions and O-H center dot center dot center dot O hydrogen bonds. Moreover, both compounds exhibit catalytic properties on degradation of methyl orange in Fenton-like process.