The hydrothermal reaction of Ag2SO4, pyridine-3,4-dicarboxylic acid (H2PDC), LiF, and H2O led to the formation of a novel complex, [Ag-2(PDC)](n) (1). X-ray crystal structural analysis indicates that 1 has a 3D coordinated framework, which contains a mono- and dinuclear mixed 1D polymeric chain. Fluorescent analyses of 1 show intense photoluminescence at 510 nm in the solid state, suggesting potential candidates for photoactive material.