The reaction of 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) ligand with silver(I) nitrate in a 1:1 molar ratio generated a [2+2] metallocyclic complex [Ag 2 (bib) 2 ](NO 3 ) 2 ·2H 2 O, in which bib ligand displayed in cis configuration. When the additional competing ligands/counterions, such as oxlate salt, 1,2-diaminoethene (en), 1,3-diaminopropane (pn), NO2- and VO3- were introduced, respectively, to the above-mentioned reaction solution, ring-open polymerization of sliver(I) complexes {[Ag(bib)]NO 3 ·H 2 O} n (1), {[Ag(bib) 2 ]X} n (X=NO3- (2), ClO4- (3)), {[Ag 2 (bib) 2 (NO 2 )](NO 2 )·19/8H 2 O} n (4) and {[Ag 2 (bib) 2 ](V 4 O 12 ) 0.5 ·3H 2 O·2MeCN} n (5) were generated. In compounds 1, 4 and 5, bib ligand adopts trans configuration and twists around the Ag–Ag axis, giving rise to single-stranded helical structure with short adjacent Ag⋯Ag distances of 3.56, 3.56, 3.50 and 3.63Å, respectively. Compounds 2 and 3 are 1D coordination polymers fusing the [2+2] metallocycle [Ag 2 (bib) 2 ] 2+ , in which bib ligand exhibits in cis configuration and the metallocycles have longer Ag⋯Ag distances of 8.52Å in 2 and 8.61Å in 3 along with the strong intracyclicπ–π interactions between phenyl groups. Cis and trans configurations of bib coexist in solution and crystallize in complexes 1 and 2 in the solid state in the presence of en or pn. The solution of 1 and 2 can be converted into 3 via the addition of the bulky ClO4- counter anion or into 4 through introduction of the competing ligand/conuterion NO2-.