The influence of the structural parameters of Cu2O2 core On magnetic coupling is studied in model alkoxo-bridged Cu(II) dimers using the density functional method and the broken symmetry approach. The effect of the hinge distortion of the bridge and the out-of-plane displacement of alkoxo group is also analyzed. A small Cu-O-Cu angle, a large Cu-O distance, the hinge distortion and the out-of-plane displacement are all the factors that can enhance the ferromagnetic character. The asymmetry at the Cu2O2 backbone affects the magnetic coupling slightly. Spin polarization may exist in weak antiferro- or ferromagnetic systems.