We observed lower shifted v(NH) bands and higher shifted 2 gamma(NH) overtone vibrations in [Cu(Hbim)(2)](n) (1) (Hbim(-) = mono deprotonated 2,2’-biimidazolate) in FT-IR spectroscopy. This observation demonstrated that complex 1 forms a hydrogen-bonding polymer with intermolecular NH-N hydrogen bonds between Hbim(-) ligands to give a one-dimensional linear structure.