Three new polyoxovanadate-based metal-organic polyhedra (VMOPs) have been successfully synthesized and structurally characterized. Single crystals of three VMOPs were obtained by reaction of VCl3 and different carboxylate ligands (2,5-H(2)TDA = thiophene-2,5-dicarboxylic acid for VMOP-4, m-H2BDC = 1,3-benzenedicarboxylic acid for VMOP-5, 2,6-H2NDC = 2,6-naphthalenedicarboxylic aid for VMOP-6) under solvothermal conditions. Though all of the three hybrids feature the same {(VV4IV)-V-V} units, their structures exhibit differences changing from truncated triangular prism to truncated quadrangular prism to octahedron, mainly depending on the nature of carboxylate ligands. Furthermore, the magnetic investigations reveal that VMOP-4-6 show similar ferromagnetic behaviors.