A tetra-n-butylammonium (TBA) salt of [H(4.5)(Ta(6)O(19))](3.5-) was synthesized by reacting hydrous tantalum oxide with TBAOH. X-ray structural analysis of TBA(3.5)[H(4.5)(Ta(6)O(19))]·2THF·5.5H(2)O (THF = tetrahydrofuran) revealed that this compound consists of a hydrogen-bonded, rod-shaped tetramer of hexatantalate that is almost 30 Å long together with TBA cations and solvent molecules of crystallization [a = 20.6354(5) Å, b = 25.5951(7) Å, c = 37.2058(8) Å, α = 77.092(1)°, β = 86.177(1)°, γ = 88.683(1)°, V = 19110.9(8) Å(3), Z = 8, and space group P ̅1]. (1)H NMR spectra showed that this tetrameric structure is maintained in solution.