The reaction of diethylenetriamine (dien) and 1,2-bis(1,2,4-triazole-1-yl)ethane (btrz) with Cu(ClO4) · 6H2O forms [Cu(dien)(btrz)(ClO4)2] (1), and the reaction of [Cu(en)2(ClO4)2] (en = ethylenediamine) with btrz forms [Cu(en)2(btrz)(ClO4)2] (2). Complexes (1) and (2) were characterized by elemental analysis, i.r., electronic spectroscopy, e.s.r. and magnetic susceptibility. Their crystal structure was determined by X-ray diffraction. In complex (1), Cu is coordinated by a dien and two btrz, forming a distorted CuN5 square pyramid with one btrz bound at the apical position. In complex (2), Cu is coordinated by two en and two nitrogen atoms of btrz forming an elongated octahedron. Both complexes have a one-dimensional chain structure in which btrz ligands bridge between pairs of Cu atom.