Abstract A new polyoxovanadate‐based metal‐organic polyhedron, termed V‐MOP‐19, constructed from pentanuclear {V 5 O 9 Cl} clusters and 1,4‐naphthalenedicarboxylic acid linkers, was successfully fabricated via the solvothermal method. Structural analysis revealed that V‐MOP‐19 adopts the cubic symmetry featured with an octahedral pore cage of 15.7 Å. Full characterization of V‐MOP‐19 was measured by Fourier transform infrared (FT‐IR), Raman spectroscopy, powder X‐ray diffraction (PXRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray (EDX), transmission electron microscopy (TEM), thermogravimetric and differential scanning calorimetry analysis (TGA‐DSC), N 2 sorption isotherm and elemental analysis (EA). The band gap energy of V‐MOP‐19, measured by UV‐Vis diffuse reflectance spectroscopy (UV‐Vis/DRS), is determined to be 2.38 eV. Moreover, the cyclic voltammetry investigation confirms a high correspondence of the band gap value (2.41 eV) with the mentioned UV‐Vis/DRS study. In particular, V‐MOP‐19 exhibits a unique magnetic property with remarkable coercivity and remanent magnetization value. These findings demonstrate that V‐MOP‐19 could be used as a potential candidate in further photocatalytic and magnetic investigations.