A new μ-oxo-bridged Cu(II) complex with cubane-like tetranuclear copper(II) complex, [Cu4(L1)4] · 4H2O (1) (H2L1 = 2-(3-methoxy-salicylidene-amino)-benzyl-alcohol), has been prepared, and structurally characterized by X-ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n and has a tetranuclear core of Cu4O4. The temperature dependence of magnetic susceptibility measurements shown that complex 1 exhibits a strong antiferromagnetic interaction with J = −103.4 cm−1.