Two diethynylpyridines with different geometries were utilized to synthesize silver pyridyldiethynide complexes in order to investigate the relation between the structure of the coordination network and the geometry of the ligand as well as counter anion. Reactions of 2,5-diethynylpyridine with CF₃CO₂Ag and AgNO₃ afforded [Ag₂(2,5-C₂PyC₂)·4CF₃CO₂Ag] (1) and [Ag₂(2,5-C₂PyC₂)·3AgNO₃] (2), respectively, and a reaction of 2,6-diethynylpyridine with CF₃CO₂Ag gave [Ag₂(2,6-C₂PyC₂)·3CF₃CO₂Ag] (3). X-Ray crystallographic studies revealed that in 1, 2,5-pyridyldiethynide groups as linkers connect silver chains to form a 2D organometallic network, and are further bridged by CF₃CO₂⁻ anions to generate a 3D network, but in 2, 2,5-pyridyldiethynide groups link novel 2D silver layers to afford a 3D organometallic network. In 3, 2,6-pyridyldiethynide groups connect Ag₁₀ units to generate an organometallic chain as bridging ligands, which are further linked by CF₃CO₂⁻ ligands to form a 2D network. It is demonstrated that both the geometry of the ligand and coexisting anions are important factors that influence the structures of coordination networks based on silver pyridyldiethynide complexes.