A novel decavanadate with organic cations, (HImz)12(V10O28)2·3H2O (Imz: Imidazole), has been synthesized in aqueous solution and characterized by IR, Raman and UV–Vis spectroscopies and single crystal X-Ray diffraction. The asymmetric unit of (HImz)12(V10O28)2·3H2O is composed of two decavanadates [V10O28]6− anions, twelve imidazolium (C3H5N2)+ cations and water molecules. The cohesion is provided by two types of bonds: hydrogen bonds O–H---N, O–H---O and N–H---O involving water molecules and organic molecules, and Vander Waals bonds for the connection between the organic molecules. The IR and Raman spectra proved the presence of organic cations, decavanadate (V10O28)6− groups and water molecules. The UV–Vis diffuse reflectance spectrum shows that this compound exhibits semiconducting behavior with an optical band gap of 2.54 eV. TGA curves indicate that the weight loss of this compound can be divided into four stages.