This paper presents novel and distinctive organosilver polymers with intriguing structure motifs, constructed from iodoacetonitrile (L1), 1-(isocyanidomethyl)-1H-benzotriazole (L2), 1,3-bis(dicyanomethylidene)indan (L3), and silver(I) salts, respectively. Treatment of L1 with AgClO4 generated [Ag(L1)(ClO4)]n (1), whose X-ray determination revealed a 2-D wavy sheet structure with square grids. Reaction of L2 with AgPF6 gave rise to a novel 2-D wavy interwoven network, ([Ag(L2)(PO2F2)0.5])n (2). The complex [Ag2(L3)2]n (3) obtained by reaction of AgClO4 with L3 can be regarded as unprecedented 3-D 5-fold interpenetrating nets with columnar aromatic stacks and indicates semiconductive behavior. The IR, ESR spectroscopic results, conductivities, and structural features of the complexes are discussed, respectively. The present findings may provide insight into the coordination versatility of silver(I) and polynitrile ligands and an inspiration for the self-assembly of novel supramolecular networks with multifunctional ligands. Crystal data: 1, C2H2AgINClO4, orthorhombic, Pca2(1) (No. 29), a = 14.503(1) A, b = 5.104(2) A, c = 10.2019(9) A, Z = 4; 2, C8H6AgN4PF4O, orthorhombic, Pnna (No. 52), a = 12.2705(3) A, b = 21.150(1) A, c = 10.040(1) A, Z = 8; 3, C30H10Ag2N8, triclinic, P1 (No. 2), a = 14.920(2) A, b = 11.896(2) A, c = 7.400(4) A, alpha = 86.55(2) degrees, beta = 80.87(2) degrees, gamma = 74.47(1) degrees, Z = 2.