The dinuclear doubly azole-bridged copper(II) complexes [Cu-2(II)(L)(2)(MeCN)(4)](ClO4)(4)center dot 3.73MeCN center dot 0.80H(2)O and [Cu-2(II)(L)(6)](ClO4)(4).solvent (solvent = 2MeCN center dot H2O; 2MeCN center dot 2H(2)O; 1.5MeOH center dot 3.5H(2)O) were prepared [L = 3-(6-m ethyl-2-pyridyl)- [1,2,4] triazolo [4,3-a]pyridine]. Structural characterizations revealed very different local geometries about the copper(II) ions, being trigonal bipyramidal for the former (tau = 0.76) and square pyramidal for the latter (tau = 0.07, 0.15, 0.07) complex. Magnetic measurements of bulk material [Cu-2(II)(L)(2)(H2O)(4])(ClO4)(4) and [Cu-2(II)(L)(6)](ClO4)(4)center dot 2H(2)O revealed antiferromagnetic coupling in both complexes, however, of very different strengths. Electron paramagnetic resonance (EPR) spectroscopy was applied to investigate magnetic properties of the complexes in detail. These experimental findings were supported by broken-symmetry DFT calculations. Systematic magneto-structural correlations are discussed.