A new tetra-Zr-substituted tungstophosphate (TP), [H2N(CH3)2]6Na6H8{Zr2[SbP2W4(OH)2O21][α2-PW10O38]}2·50H2O (1), has been made by the hydrothermal reaction of the [B-α-SbW9O33]9- building block with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and NaOAc-HOAc (pH = 4.8), and further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), 31P NMR spectroscopy and single-crystal X-ray diffraction. 1 is a toroidal structure formed by two divacant [α2-PW10O38]11- units and two [SbP2W4(OH)2O21]7- fragments linked by four Zr4+ cations. Note that the TP is reassembled with tetrahedral PO4 replacing the triangular pyramidal SbO3 in the [B-α-SbW9O33]9- precursor. In addition, the pendant SbO3 derives from the dissociation of the [B-α-SbW9O33]9- precursor. Furthermore, the electrochemical properties of 1 have been studied in Na2SO4 + H2SO4 supporting electrolyte (0.5 mol L-1), and indicate that 1 exhibits apparent catalytic activity toward H2O2 and BrO3- reduction. The 31P NMR spectrum of 1 exhibits three signals with approximately proportional intensities, which is consistent with the solid-state structure.