A new ternary complex [Cu(glygly)(AMBZ)(H 2 O)]ClÁH 2 O (1) (glygly ¼ glycylglycine anion, AMBZ ¼ 2-aminomethylbenzimidazole) has been prepared and characterized by single-crystal X-ray diffractometry and ESR, electronic and IR spectroscopy. The copper(II) ion has a slightly distorted square-pyramidal coordination, being equatorially coordinated by the bidentate 2-aminomethylbenzimidazole and the bidentate glycylglycine anion and axially by a water molecule. The individual complex molecules are hydrogen bonded to their neighbors, forming a polymeric hydrogen-bonded lattice. Spectroscopic data are in accordance with the crystal structure.