A new family of 10 organosilver(I) complexes, namely, [(AgC≡CPh)2(AgO2CCF3)4(cis-1,2-bix)(CH3OH)]·2CH3OH (1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, 1A), [(AgC≡CC6H4Me-2)2(AgO2CCF3)4(cis-1,3-bix)]·5.25H2O (1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene, 1B), [(AgC≡CPh)3(AgO2CCF3)6(trans-1,4-bix)(CH3OH)3]·2CH3OH (1,4-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, 2A), [(AgC≡CC6H4Me-4)3(AgO2CCF3)6(trans-1,4-bix)(CH3OH)3]·2CH3OH (2B), [(AgC≡CPh)(AgO2CCF3)3(trans-1,3-bix)(H2O)]·0.5H2O (3A), [(AgC≡CC6H4Me-4)(AgO2CCF3)3(trans-1,3-bix)(H2O)] (3B), [(AgC≡CC6H4Me-4)(AgO2CCF3)3(bbi)(H2O)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole), 3C), [(AgC≡CC6H4tBu-4)(AgO2CCF3)3(trans-1,4-bix)] (3D), [(AgC≡CPh)2(AgO2CCF3)4(bbi)(H2O)]·2H2O (4), and [(AgC≡CtBu)2(AgO2CCF3)4(bbi)] (5), have been synthesized employing a variable combination of ethynide, trifluoroacetate, and bridging bis(imidazole) ligands. In both 1A and 1B, the flexible 1,2-bix or 1,3-bix ligands in cis-conformations are alternatively attached on both sides of an infinite cationic silver(I) chain, and neighboring organosilver(I) chains are further interconnected by intermolecular hydrogen bonds to generate a three-dimensional supramolecular architecture. In structural analogues 2A and 2B, pairs of silver(I) chains are linked via the trans-1,4-bix ligands to yield infinite ladders, which are further joined together by hydrogen bonds to afford a three-dimensional supramolecular network. In the isostructural series 3A–3D, centrosymmetric (PhC2)2Ag8 aggregates are connected by trifluoroacetate groups to give an infinite chain, and such chains are then bridged by bis(imidazole) ligands to generate a coordination layer. Furthermore, adjacent layers are linked by hydrogen bonds to form a three-dimensional supramolecular network. In 4, infinite silver(I)–phenylethynide chains constructed by Ag6 aggregates are bridged by bbi ligands in a gauche–trans–gauche conformation to yield a three-dimensional coordination framework. In contrast, infinite silver(I)-tert-butylethynide chains based on Ag8 and Ag6 aggregates in 5 are linked by bbi ligands exhibiting different trans–trans–trans and gauche–trans–gauche conformations to generate a three-dimensional coordination network. Finally, the roles played by various bis(imidazole) ligands and ethynides bearing different substituents in the framework assembly are discussed in detail.