A new organic-inorganic hybrid heteropolyoxoniobate, [{Cu(en)(H2O)4}{Cu(en)2(H2O)}{Cu(en)2(H2O)2}]1.5[H8SiTe8Nb15O64]·6H2O (1; en = ethanediamine), has been successfully synthesized by a conventional method. The compound was directed by pairs of [TeO3]2-/[SiO3]2- ions, generating two novel {TeNb9} and {SiTeNb6} subunits in situ owing to the mixed heteroanion. In addition, the solution behavior of compound 1 was investigated.