Reaction of Ph3Bi[O(O)CC5H4N‐3]2 (1) in CHCl3 and AgClO4 in ethanol, in 1:1 molar ratio, afforded the isolation of colorless crystals of a coordination compound which was proved to be [Ag(EtOH){Ph3Bi[O(O)CC5H4N-3]2}(ClO4)]•CHCl3 (2•CHCl3) by single-crystal X-ray diffraction. A 1D coordination polymer is formed based on bridging triphenylbismuth(V) di(nicotinate) between silver atoms, with trans Ag−N dative bonds [2.183(4), 2.196(5) Å]. Additional Ag•••O interactions are established between the coinage metal atom and an ethanol molecule [2.58(3) Å] as well as a perchlorate anion [2.746(6) Å], respectively. Its supramolecular architecture, based on a variety of non-covalent interactions, i.e. O−H•••O, C−H•••O or C−H•••Cl hydrogen bonds, π•••π , C−H•••π, C−Cl•••π interactions, as well as Ag•••O and Ag•••Cl contacts, is discussed.