A one-dimensional Ag(I) coordination complex, catena-poly[[silver(I)-μ-{2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol-κ(2)N(2):N(3)}] perchlorate monohydrate], {[Ag(C19H15N3O)]ClO4·H2O}n, was synthesized by the reaction of 2-[2-(pyridin-4-yl)-1H-benzimidazol-1-ylmethyl]phenol (L) with silver perchlorate. In the complex, the L ligands are arranged alternately and link Ag(I) cations through one benzimidazole N atom and the N atom of the pyridine ring, leading to an extended zigzag chain structure. In addition, the one-dimensional chains are extended into a three-dimensional supramolecular architecture via O-H···O hydrogen-bond interactions and π-π stacking interactions. The complex exhibits photoluminescence in acetonitrile solution, with an emission maximum at 390 nm, and investigation of the thermal stability reveals that the network structure is stable up to 650 K.