The hydrothermal reaction of Cu(acetate)2 and K3[Fe(CN)6] with 5-phenyl-2,2′-bipyridine (5-ph-2,2′-bpy) in water yields the polymeric title complex, [Cu5(CN)5(C16H12N2)3]n, which consists of ribbons along the a axis, constructed from 26-membered {Cu10(CN)8} rings. In these rings, the metal atoms are bridged by cyanide groups, except for one close Cu⋯Cu contact [2.7535 (12) Å], which can be considered as ligand-unsupported. Within the rings, one Cu atom has a distorted tetrahedral geometry through the coordination to two N atoms from 5-ph-2,2′-bpy and two N/C atoms from two cyanide groups. Two Cu atoms have a trigonal planar environment being coordinated by three cyanide groups and two other Cu atoms have a distorted square planar geometry through coordination to two N atoms from 5-ph-2,2′-bpy and two N/C atoms from two cyanide groups.