A new tellurate, NaBiTeO 5 has been synthesized by standard solid-state techniques using Na 2 CO 3 , Bi 2 O 3 , and TeO 2 as reagents. The structure of NaBiTeO 5 was determined by single crystal X-ray diffraction. NaBiTeO 5 crystallizes in the monoclinic space group P2 1 /c (No. 14), with a=7.2645(5), b=9.8048(6), c=6.2718(4) Å, β=106.819(1) o , V=427.61(5) Å 3 and Z=4. NaBiTeO 5 has a novel three-dimensional framework consisting of chains of [TeO 6 / 2 ] 0 octahedra that are linked by [BiO 4 / 2 ] - polyhedra. Bi 3 + is in an asymmetric coordination environment attributable to its lone-pair. The lone-pair on the Bi 3 + point in the [100] and [00-1] directions and interacts with the Na + cation. Infrared and thermogravimetric analyzes are also presented.