A new asymmetric ligand, 5-{3-[5-(4-methylphenyl)-1,3,4-oxadiazol-2-yl]phenyl}-2-(pyridin-3-yl)-1,3,4-oxadiazole (L5), which contains two oxadiazole rings, was synthesized and characterized. The assembly of symmetric 2,5-bis(pyridin-3-yl)-1,3,4-oxadiazole (L1) and asymmetricL5with AgCO2CF3in solution yielded two novel AgIcomplexes, namelycatena-poly[[di-μ-trifluoroacetato-disilver(I)]-bis[μ-2,5-bis(pyridin-3-yl)-1,3,4-oxadiazole]], [Ag2(C2F3O2)2(C12H8N4O)2]nor [Ag2(μ2-O2CCF3)2(L1)2]n(1), and bis(μ3-5-{3-[5-(4-methylphenyl)-1,3,4-oxadiazol-2-yl]phenyl}-2-(pyridin-3-yl)-1,3,4-oxadiazole)tetra-μ3-trifluoroacetato-tetrasilver(I) dichloromethane monosolvate, [Ag4(C2F3O2)4(C22H15N5O2)2]·CH2Cl2or [Ag2(μ3-O2CCF3)2(L5)]2·CH2Cl2(2). Complex1displays a one-dimensional ring–chain motif, where dinuclear Ag2(CF3CO2)2units alternate with Ag2(L1)2macrocycles. This structure is different from previously reported Ag–L1complexes with different anions. Complex2features a tetranuclear supramolecular macrocycle, in which each ligand adopts a tridentate coordination mode with the oxadiazole ring next to thep-tolyl ring coordinated and that next to the pyridyl ring free. TwoL5ligands are bound to two Ag1 centres through two oxadiazole N and two pyridyl N atoms to form a macrocycle. The other two oxadiazole N atoms coordinate to the two Ag2 centres of the Ag2(O2CCF3)4dimer. Each CF3CO2−anion adopts a μ3-coordination mode, bridging the Ag1 and Ag2 centres to form a tetranuclear silver(I) complex. This study indicates that the donor ability of the bridging oxadiazole rings can be tuned by electron-withdrawing and -donating substituents. The emission properties of ligandsL1andL5and complexes1and2were also investigated in the solid state.