Two new bent bis(cyanophenyl)oxadiazole ligands, 2,5-bis(4-cyanophenyl)-1,3,4-oxadiazole (L7) and 2,5-bis(3-cyanophenyl)-1,3,4-oxadiazole (U), were synthesized. The coordination chemistry of these ligands with various Ag(I) salts has been investigated. Seven new coordination polymers, namely, {[Ag(L7)(H2O)]ClO4}(n) (1) (triclinic, P1, a = 9.342(4) angstrom, b = 9,889(4) angstrom, c = 10.512(4) angstrom, alpha = 68.978(6)degrees, beta = 78.217(6)degrees, gamma = 81.851(7)degrees, Z = 2), {[Ag(L7)]SO3CF3}(n) (2) (monoclinic, P2(1)/n, a = 7.559(2) angstrom, b = 23.739(6) angstrom, c = 10.426(3) angstrom, beta = 108.071(4)degrees, Z = 4), {[Ag(L8)]BF(4)center dot 0.5(C6H6)-H2O}(n)(3) (triclinic, P1, a = 7.498(3) angstrom, b = 10.649(4) angstrom, c = 13.673(5) angstrom, alpha = 98.602(5)degrees, beta = 100.004(5)degrees, gamma =110.232(5)degrees, Z = 2), {[Ag(L8)SbF6]center dot H2O}(n) (4) (triclinic, P1, a = 8.2621 (9) angstrom, b = 10.6127(12) angstrom, c = 13.3685(15) angstrom, alpha = 98.012(2)degrees, beta = 106.259(2)degrees, gamma = 112.362(2)degrees, Z = 2), {[Ag-2(L8)(2)(SO3CF3)]center dot H2O}(n) (5) (triclinic, P1, a = 10.713(4) angstrom, b = 13.449(5) angstrom, c = 15.423(5) angstrom, alpha = 65.908(5)degrees, beta = 74.231(5)degrees, gamma = 83.255(5)degrees, Z = 2), {[Ag-2(L8)(C6H6)(ClO4)]center dot ClO4}, (6) (monoclinic, P2(1)/n, a = 6.9681(17) angstrom, b = 20,627(5) angstrom, c, = 17.437(4) angstrom, beta = 95.880(4)degrees, Z = 4), and {[Ag-2(L8)(H2PO4)(2)]}(n) (7) (triclinic, P1, a = 7.956(2) angstrom, b = 9.938(3) angstrom, c = 14.242(4) angstrom, alpha = 106.191(4)degrees, beta = 97.322(4)degrees, gamma = 107.392(4)degrees, Z = 1), were obtained by the combination of L7 and L8 with Ag(I) salts in a benzene/methylene chloride mixed-solvent system and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the luminescence and electrical conductance properties of compounds 1-6 and the host-guest chemistry of compound 3 were investigated.