A novel diperoxovanadate complex NH4[OV(O2)2{2-(2'-pyridyl)-imidazole}] x 4H2O was synthesized in aqueous solution under physiological conditions. The solution structure of the complex was characterized by multinuclear (1H, 13C, 14N, and 51V) as well as multi-dimensional (DOSY and C-H COSY) NMR techniques in the interaction system of NH4VO3/H2O2/2-(2'-pyridyl)-imidazole at room temperature. The crystal structure of the complex was determined at 173K by single-crystal X-ray diffraction method. It belongs to the monoclinic space group P21/c with a = 13.048(4), b = 6.984(2), c = 17.814(5) A, beta = 104.695(5), V = 1570.3(8) A3 and Z = 4. The crystal is composed of ammonium ions, {2-(2'-pyridyl)-imidazole}oxodiperoxovanadate(V) ions, and water molecules, which are held together by ionic and hydrogen bond forces. The metal atom in the complex is seven-coordinated with a distorted pentagonal bipyramidal geometry. It is the first mononuclear diperoxovanadate complex with a N, N'-chelating biheteroaromatic ligand and its 51V chemical shift is at the highest field among the known mononuclear diperoxovanadate(V) complexes.