A new one-dimensional tellurite phosphate, Ba 2 TeO(PO 4 ) 2 has been synthesized by standard solid-state reaction techniques using BaCO 3 , TeO 2 , and (NH 4 )H 2 PO 4 as reagents. The structure of Ba 2 TeO(PO 4 ) 2 was determined by single-crystal X-ray diffraction. Ba 2 TeO(PO 4 ) 2 crystallizes in the triclinic space group P-1 (No. 2), with a=6.9461(16)Å, b=7.3970(17)Å, c=8.887(2)Å, α=76.843(4)°, β=79.933(4)°, γ=75.688(4)°, V=427.40(17)Å3, and Z=2. Ba 2 TeO(PO 4 ) 2 has a novel one-dimensional chain structure that is composed of PO 4 tetrahedra and TeO 5 polyhedra. Te 4+ cations are in asymmetric coordination environments attributable to their lone pairs. The lone pairs on the Te 4+ cations point in the [100] and [−100] direction and interact with the Ba 2+ cations. Infrared, Raman, and UV–Vis diffuse reflectance spectroscopy, thermogravimetric analysis, and dipole moment calculations are also presented.