Colorless crystals of the coordination polymer (CP) [Ag5(CN)5(2,2′-bpy)2]n, 1 were obtained by the reaction of AgNO3, 2,2′-bipyridine (2,2′-bpy) and KCN. The crystal structure of 1 consists of 1D-puckered AgCN chains which are decorated by 2,2′-bpy molecules. These chains form 2D-fused deformed six-membered rings; [Ag4(CN)2(2,2′-bpy)2] creating wide voids capable to accommodate the 2,2′-bpy molecules. 3D-network structure is created via H-bonds, π-π stacking and Ag-Ag interaction. The structure of the CP 1 was characterized by IR, UV-visible, TGA, NMR spectra and X-ray single crystal analysis. The CP 1 was used as heterogeneous catalyst for the oxidative discoloration of methylene blue dye (MB) by H2O2.