Two silver( I) coordination complexes of 1,10-phenanthroline-5,6-dione (pdon), [Ag-2(pdon)(2)(ClO4)(2)] (1) and [Ag( pdon)(2)](CF3SO3) (2), have been synthesized and characterized by elemental analysis, IR, and X-ray diffraction analysis. Using AgClO4 with pdon, the central silver(I) is bridged by ligand pdon with two N and one O atoms and lead to the one-dimensional (1D) chain structure in 1. When triflate anion is used as a counter ion in 2, the silver(I) is chelated by two ligands with four N atoms, and then the molecular unit is linked by intermolecular hydrogen bond to afford a novel two-dimensional (2D) network architecture.