The hydrothermal reaction of NaVO3.H2O, barbituric acid, NH2NH2.2HCl, H3PO4, and H2O gave a novel heteropolyoxovanadate Na-6[((PO4)-O-V)(V6V12O39)-V-V-O-IV](2).H3PO4.31H(2)O (1) and an unexpected phase Na-2[C12H6N6O9].7H(2)O (2). The basic building blocks in 1 are the six-capped sphere-shaped heteropoly anion [((PO4)-O-V)(V6V12O39)-V-V-O-IV](3-) with framework similar to that of the reported polyoxovanadates possessing {V18O42} clusters encapsulating VO4 or other ions. These heterpoly anionic units are linked via V-O-V bridges into an interesting 3D straight-channel structure. The structure of 2 consists of novel organic anions ([C12N6H6O9](2-), 5,5-bis(2',4', 6'-trioxopyrimidyl) barbital, representing the first oxidized barbituric acid trimer) linked via sodium ions into 1 D hollow tubes with diameter of 4.49 x 6.86 Angstrom and further connected into a three-dimensional framework via hydrogen bonds.