The Tb coordination complex [Tb(H₂O)₈]?(L)?2(4,4'?bipy)?3H₂O（complex 1） was synthesized by hydrothermal reaction of sodium 1,3,6?naphthalene trisulfonate (Na₃L) and 4,4'?bipy (4,4'?bipy) with Tb(NO₃)₃?6H₂O. The molecular structure and composition of complex 1 were characterized by single crystal X?ray diffraction, FT?IR spectroscopy, thermogravimetric analysis and elemental analysis. Thermal stability and fluorescence emission properties of complex 1 were also evaluated. The results indicate that Tb³⁺ is eight?coordinated in a tetragonal antiprismatic coordination configuration and coordinates with eight H₂O molecules to form [Tb(H₂O)₈]³⁺.L^3- does not coordinate with metal ion, but only balances the positive charge in the molecule. The formation of hydrogen bonds between the sulfonic acid group of the L^3- and the coordinating H₂O molecule connects the [Tb(H₂O)₈]³⁺ and the L^3- to form a one?dimensional chain structure,which in turn expands into a two?dimensional lamellar structure.The fluorescence emission peaks of complex 1 at 395，453 nm are the characteristic peaks of Na₃L, and the emission peaks at 545,601，641 nm are the characteristic peaks of Tb³⁺.