Polyoxometalates possess remarkable structural diversity and exhibit wide range of properties with wide-ranging applications in fields such as luminescence, magnetism, medicine, electrochemistry, catalysis, and material science. By the introduction of a heteroatom to a polyoxometalate framework, further diversification can be achieved and the resulting heteropolyoxometalates exhibit a numerous examples of attractive catalytic applications. Vanadate clusters in aqueous solutions have been studied extensively, and the reported structures include (V3O9) 3- , (V5O14) 3- , (V8O14) 4- ,(V12O32) 4- , (V13O34) 3- , (V15O42) 9- , and (H2V16O39) 7- anions. Thus far, most polyoxovanadates have been synthesized in aqueous solution or under hydrothermal conditions, which may limit further research in this area. New synthetic routes, especially those in organic media with soluble vanadium precursors, present an unusual approach, for they may lead to the design and construction of new vanadate clusters containing different motifs and frameworks. Herein we present the synthesis, structural characterization and magnetic properties of a new class of lanthanide containing heteropolyoxovanadates with „chocolate“-like structures [Ln2(H2O)8V12O32(Cl)]Cl where Ln = Gd, Eu, Dy, Tb and Er.formulaFigure 1. Molecular fragment of "chocolate”-like cation [Dy2(H2O)8V12O32(Cl)]+ (left). Solvent molecules, hydrogen atoms and chloride-anion were omitted for clarity.