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 (L8), 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, P1h, a=9.342(4) Å, b=9.889(4) Å, c=10.512(4) Å, R=68.978(6)°, β=78.217(6)°, ç=81.851(7)°, Z=2), {[Ag(L7)]SO3CF3}n (2) (monoclinic, P21/n, a=7.559(2) Å, b=23.739(6) Å, c=10.426(3) Å, β=108.071(4)°, Z=4), {[Ag(L8)]BF4β0.5(C6H6)βH2O}n(3) (triclinic, P1h, a=7.498(3) Å, b=10.649(4) Å, c=13.673(5) Å, R=98.602(5)°, β=100.004(5)°, ç )110.232(5)°, Z=2), {[Ag(L8)SbF6]βH2O}n (4) (triclinic, P1h, a=8.2621(9) Å, b=10.6127(12) Å, c=13.3685(15) Å, R=98.012(2)°, β=106.259(2)°, ç=112.362(2)°, Z=2), {[Ag2(L8)2(SO3CF3)]βH2O}n (5) (triclinic, P1h, a=10.713(4) Å, b=13.449(5) Å, c=15.423(5) Å, R) 65.908(5)°, β=74.231(5)°, ç=83.255(5)°, Z=2), {[Ag2(L8)(C6H6)(ClO4)]βClO4}n (6) (monoclinic, P21/n, a=6.9681(17) Å, b=20.627(5) Å, c=17.437(4) Å, β=95.880(4)°, Z=4), and {[Ag2(L8)(H2PO4)2]}n (7) (triclinic, P1h, a=7.956(2) Å, b=9.938(3) Å, c=14.242(4) Å, R=106.191(4)°, β=97.322(4)°, ç=107.392(4)°, Z=1), were obtained by the combination of L7 and L8 with Ag(I) salts in a benzene/methylene chloride mixedsolvent 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.