Two cyanide-bridged W-V-M [M = Mn-III (1), Co-II (2)] bimetallic clusters were prepared by self-assembling a new molecular precursor [W(CN)(6)(bpy)](-) and the corresponding metal complexes. Compound 1 shows a tetranuclear W2Mn2 entity, consisting of a Jahn-Teller ion, Mn-III, which serves as an anisotropic source, while compound 2 exhibits a trimeric W2Co structure. Among them, compound 1 displays slow relaxation of the magnetization, which is typical of a single-molecule magnet behavior.