Based on the N-donor auxiliary ligand effect, four new silver(I) coordination polymers derived from 2,6-naphthalenedicarboxylic acid (H 2 ndc), namely [Ag(L1)-(ndc) 0.5 ] n (1), [Ag(L2)(ndc) 0.5 ] n (2), {[Ag(L3)(ndc) 0.5 ]Á 0.5(H 2 ndc)} n (3), and [Ag(L4)(H 2 O)ÁHndc] n (4) (L1 = 1,3-bis(thiabendazole)butane, L2 = 4,4 0 -bis(pyrazole-1-ylmethyl)-biphenyl, L3 = 1,4-bis(benzimidazole)butane, L4 = 4,4 0 -dipyridylamine), have been synthesized by solvothermal reactions. Complex 1 possesses a 1D infinite loop and chain, which is further extended into a 3D supramolecular framework by p-p stacking interactions. Complex 2 presents an unprecedented 3D (3,4)-connected lim (baa-e-3,4-Imma) topology with the Schläfli symbol of (4.10 2 )2(4 2 .10 4 ). Complex 3 exhibits a 2D three-connected hcb (Shubnikov hexagonal plane) network and the Schläfli symbol is (6 3 ). Complex 4 shows a 1D linear chain, which generates a 2D supramolecular layer via hydrogen bonding interactions. Solid-state properties of 1-4 have also been investigated, which display high thermal stability and intense fluorescent emission in solid state. Moreover, the complexes manifest excellent catalytic activities for the decomposition of Congo red azo dye by hydrogen peroxide in a Fenton-like process.