TbCu(TeO3)2Cl was obtained in high yield from high temperature solid-state reac-ion of Tb4O7,CuO,CuCl2 and TeO2 in a 1:2:2:8 molar ratio at 710 ℃ in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. The title compound crystal-lizes in monoclinic,space group P21/c,with a=5.409(2),b=14.994(6),c=9.183(4),β= 98.884(5)°,V=735.8(5) ?3 and Z=4. TbCu(TeO3)2Cl is isostructural with LnCu(TeO3)2X (Ln= Dy,X= Cl; Ln=Er,X=Cl,Br). Its structure features a three-dimensional (3D) network built from Tb(Ⅲ) and Cu(II) ions interconnected by tellurite and chloride anions; the chloride anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels in the network. Solid-state luminescent spectrum of TbCu(TeO3)2Cl shows a strong emission band at 545 nm with a luminescent life time of 291 μs.