Abstract In this paper, four coordination polymers, {[Ag(bmi)]·NO 3 } n ( 1 ), [Co(N 3 ) 2 (bmi) 2 ] n ( 2 ), [Cu(SCN) 2 (bmi) 2 ] n ( 3 ), and {[Cu(bmi) 2 (CH 3 OH)(H 2 O)]·(ClO 4 ) 2 } n ( 4 ) have been synthesized through the reactions of an unsymmetrical ligand 1-((benzotriazol-1-yl)methyl)-1 H -1,3-imidazole (bmi) with Ag(I), Co(II) and Cu(II) salts at room temperature. X-ray diffraction analyses showed that compound 1 exhibits double-stranded helical chain. Compounds 2 – 4 display 2-D rhombus grid network structure. The rhombus grid consists of 32-membered rings, and gives the dimensions of ca. 8.9 × 8.9 A for compound 2 , ca. 10.1 × 10.1 A for compound 3 , and ca. 9.7 × 9.5 A for compound 4 . In addition, the 2-D layers of compound 3 are stacked into 3-D structure via π – π interactions, while the 3-D architecture of compound 4 is realized through complicated hydrogen bonds and π – π interactions. The thermal analyses of compounds 1 and 3 indicate that they have high thermal stability and are stable up to 259 °C.