Two Cu(I) coordination polymers {[Cu 2 (bibp) 2 ]·bdc·3H 2 O} n ( 1 ) and {[Cu 3 (bib) 3 ]·btc·5H 2 O} n ( 2 ), where bibp = 4,4′-bis(1-imidazol-1-yl)biphenyl, H 2 bdc = terephthalic acid, bib = 1,4-bis(1-imidazol-1-yl)benzene, H 3 btc = benzene-1,3,5-tricarboxylic acid, are synthesized under solvothermal conditions and characterized structurally. Complex 1 crystallizes in the triclinic form with the space group P -1, and Cu(1) is two-coordinated by two N atoms of bibp, Cu(2) is three coordinated from two N atoms of bibp and one water molecule. Complex 2 crystallizes in the triclinic form with the space group P -1; the copper ions are monovalent and two-coordinated by two N atoms of bib. The bdc and btc ligands are not coordinated with Cu ions, but play important roles in the generation of a 3D supramolecular structure of complexes 1 and 2 via weak interactions respectively.