We report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [Cu^II(phen)₃]₂{[Cu^II(phen)₂]₂[W^V(CN)₈]₂}(ClO₄)₂·10H₂O (phen = 1,10-phenanthroline) (<b>1</b>) and {[Cu^II(bpy)₂]₂[W^V(CN)₈]} {[Cu^II(bpy)₂][W^V(CN)₈]}·4H₂O (bpy = 2,2′-bipyridyl) (<b>2</b>). Compound <b>1</b> consists of cyano-bridged [Cu^II₂W^V₂]²⁻ molecular rectangles and isolated [Cu^II(phen)₃]²⁺ complexes. The molecular structure of <b>2</b> reveals cyano-bridged trinuclear [Cu^II₂W^V]⁺ and dinuclear [Cu^IIW^V]⁻ ions. Magnetic interactions in <b>1</b> are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic Cu^II−NC−W^V units (<i>J</i>₁ = +39(4) cm⁻¹) interacting antiferromagnetically (<i>J</i>₂ = −1.6(4) cm⁻¹). The analysis of the magnetic response of <b>2</b> reveals ferromagnetic interaction within the [Cu^II−NC−W^V−CN−Cu^II]⁺ and [Cu^II−NC−W^V]⁻ isolated units, characterized by <i>J</i> = +35(7) cm⁻¹ and antiferromagnetic coupling between them (4<i>J</i>′ = −0.30(8) cm⁻¹). The discussion of the magnetic behavior and the correlation of the <i>J</i>_CuW parameters with the geometry of cyano bridges at copper(II) centers of <b>1</b> and <b>2</b> is based on the DFT calculations, which yield <i>J</i>_av = +13.2 cm⁻¹ for <b>1</b> and <i>J</i> = +31 cm⁻¹ for <b>2</b>. The domination of the ferromagnetic Cu^II−NC−W^V interaction in <b>1</b> and <b>2</b> originates from the mutual orthogonality of natural magnetic orbitals in the case of coordination of cyano bridges at the equatorial sites of Cu(II) moieties.Read less <