A binuclear vanadium complex NH4[(VⅣO)2( Ⅲ(H2O)9] wa s synthesized by reaction of NH3VO3, nitrilotriacetic acid and EuCl3 in one aque ous solution. The crystal X-ray analysis shows that the complex contains one bin uclear vanadium anion [(VⅣO)2( -and one [EuⅢ(H2O)9]3+ cation. T he molecules are built up to a three-dimensional supramolecular structure throug h hydrogen bonding. CCDC: 238716.